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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
• • 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
• • 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
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

• the present invention relates to a thermosetting composition and a thermosetting inkjet ink. More specifically, a thermosetting composition having excellent storage stability at a high temperature and a thermosetting film surface at a high temperature and high humidity and a thermosetting composition thereof.
• the present invention relates to a thermosetting inkjet ink using.
• Poly (meth) acrylate resin (hereinafter also referred to as "acrylic resin”) has high transparency and impact resistance, and is easy to form and color thermoplastics. Therefore, it is a substitute for inorganic glass for buildings and vehicles. In addition to being used as window materials, it is also used in various applications as parts in electrical and electronic equipment, daily necessities, office supplies, etc.
• Acrylic resin can be produced by adding a radical generator that generates radicals by irradiating (meth) acrylate with active energy rays such as ultraviolet rays or electron beams and subjecting it to radical polymerization (crosslinking reaction). .. It can also be produced by radical polymerization by adding a peroxide to (meth) acrylate and heating it.
• a radical generator that generates radicals by irradiating (meth) acrylate with active energy rays such as ultraviolet rays or electron beams and subjecting it to radical polymerization (crosslinking reaction). .. It can also be produced by radical polymerization by adding a peroxide to (meth) acrylate and heating it.
• Patent Document 1 describes a curable composition used in a method for producing a poly (meth) acrylate by polymerizing a monomer having a (meth) acrylate in the presence of isocyanate.
• Patent Document 2 reports a polyurethane composition containing an acrylate having a functional group that reacts with isocyanate.
• thermosetting compositions and photocurable compositions a coating film is formed by a photolithography development method or a screen printing method to form an etching resist, a solder resist and a marking on a printed circuit board. It has been known.
• Patent Document 6 contains an acryloyl group-containing monomer, a block polyisocyanate having a triazine skeleton, and a photopolymerization initiator, and has a photocurable thermosetting composition used for printing by an inkjet method.
• Patent Document 7 describes titanium oxide, a (meth) acrylate having a hydroxy group, a photopolymerization initiator, a wet dispersant having an acid value, and a specific bifunctional (meth) acrylate compound (hydroxy group).
• a white curable composition for a printed wiring board applied to a copper wiring and a substrate including (excluding those having).
• thermosetting compositions and thermosetting inkjet inks in particular, the storage stability at high temperature and the thermosetting property of the surface of the cured film under high temperature and high humidity are not yet sufficient and have been improved. It is desired.
• the present invention has been made in view of the above problems and situations, and the problem to be solved thereof is a thermosetting composition having excellent storage stability at high temperature and thermosetting property of the surface of a cured film under high temperature and high humidity. And to provide a thermosetting inkjet ink using the same.
• the present inventor has made a block isocyanate (A) and a poly (meth) acrylate (C) in a thermosetting composition.
• A block isocyanate
• C poly (meth) acrylate
• the storage stability at high temperature can be significantly improved, and the thermosetting property of the surface of the cured film under high temperature and high humidity can be significantly improved.
• the above-mentioned problem according to the present invention is solved by the following means.
• a compound (B) having a functional group capable of hydrogen bonding with the blocked isocyanate (A) and a (meth) acryloyl group-containing monomer (C) having no functional group capable of reacting with the blocked isocyanate are contained.
• the compound (B) is contained in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acryloyl group-containing monomer (C), and the blocked isocyanate (A) is 0.1.
• thermosetting composition according to item 1 which contains a photopolymerization initiator.
• the functional group of the compound (B) capable of hydrogen bonding with the blocked isocyanate (A) is at least one selected from the group consisting of a hydroxy group, a carboxy group, an amino group and a mercapto group.
• thermosetting composition according to Item 3 wherein the compound (B) is a (meth) acryloyl group-containing monomer.
• thermosetting composition according to item 1.
• thermosetting inkjet ink containing the thermosetting composition according to any one of items 1 to 5.
• thermosetting inkjet ink according to Item 6 which contains a gelling agent and undergoes a sol-gel phase transition with temperature.
• the sol-gel phase transition is described in Item 7, wherein the viscosity at a temperature of 25 ° C. is in the range of 1 to 1 ⁇ 10 4 Pa ⁇ s, and the sol-gel phase transition occurs in the range of a temperature of 40 ° C. or higher and lower than 100 ° C.
• Thermosetting inkjet ink is described in Item 7, wherein the viscosity at a temperature of 25 ° C. is in the range of 1 to 1 ⁇ 10 4 Pa ⁇ s, and the sol-gel phase transition occurs in the range of a temperature of 40 ° C. or higher and lower than 100 ° C. Thermosetting inkjet ink.
• thermosetting inkjet ink wherein the gelling agent is a compound having a structure represented by the following general formula (G1) or general formula (G2).
• General formula (G2): R 3- COO-R 4 In the formula, R 1 to R 4 each independently represent an alkyl chain having a linear moiety having 12 or more carbon atoms and may have a branch.
• thermosetting inkjet ink according to any one of items 6 to 9, wherein the thermosetting inkjet ink is used for forming a solder resist pattern used for a printed circuit board.
• thermosetting composition having excellent storage stability at high temperature and thermosetting of the surface of a cured film under high temperature and high humidity, and a thermosetting inkjet ink using the same. it can.
• Structure 1 shows a structure in which a blocked isocyanate (A) in which a terminal isocyanate group is blocked by a blocking group is hydrogen-bonded to a compound (B) having active hydrogen.
• the blocked isocyanate (A) and compound (B) form a stable six-membered ring structure as shown in structure 1 below, thus improving storage stability at high temperatures. I presume that it can be done.
• R represents a residue of a blocked isocyanate group
• X represents an oxygen atom, a sulfur atom or a nitrogen atom.
• the curability of the cured film surface under high temperature and high humidity is also improved. This is because after the blocking agent of the blocked isocyanate (A) is removed during thermosetting, the isocyanate group reacts with the compound (B), and the R'site mainly composed of the hydrocarbon group of the compound (B) is on the outside of the molecule. It is presumed that the hydrophobicity of the surface of the cured film is increased by overhanging and easily orienting on the surface of the cured film.
• the thermosetting composition of the present invention is a thermosetting composition containing a blocked isocyanate (A), and is a compound (B) having a functional group capable of hydrogen-bonding with the blocked isocyanate (A), and a blocked isocyanate.
• the compound (B) is added to 100 parts by mass of the (meth) acryloyl group-containing monomer (C) containing the (meth) acryloyl group-containing monomer (C) having no functional group capable of reacting with. It is characterized by containing in the range of 1 to 20 parts by mass and containing the blocked isocyanate (A) in the range of 0.1 to 20 parts by mass.
• This feature is a technical feature common to or corresponding to each of the following embodiments (forms).
• the functional group of the compound (B) capable of hydrogen bonding with the blocked isocyanate (A) is at least one selected from the group consisting of a hydroxy group, a carboxy group, an amino group and a mercapto group. It is preferable because the curability of the film surface can be maintained high.
• the compound (B) is preferably a (meth) acryloyl group-containing monomer. As a result, the degree of polymerization of the entire thermosetting composition can be further improved, so that the thermosetting property can be improved.
• the compound (B) is contained in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acryloyl group-containing monomer (C). It is preferable to contain it. Further, it is preferable that the inkjet ink contains the thermosetting composition of the present invention. Further, in the present invention, it is preferable that the thermosetting inkjet ink contains a gelling agent and undergoes a sol-gel phase transition depending on the temperature. As a result, the hydrophobicity of the cured film is increased, and the effect of excellent curability of the film surface under high temperature and high humidity can be obtained. The viscosity at a temperature of 25 ° C.
• thermosetting inkjet ink of the present invention is preferably a thermosetting inkjet ink for forming a solder resist pattern used for a printed circuit board from the viewpoint of obtaining a cured film having a high surface hardness.
• (meth) acryloyl group means an acryloyl group or a meta-acryloyl group
• (meth) acrylate means an acrylate or a methacrylate
• thermosetting composition of the present invention is a thermosetting composition containing a blocked isocyanate (A), and is a compound (B) having a functional group capable of hydrogen-bonding with the blocked isocyanate (A), and a blocked isocyanate.
• the compound (B) is added to 100 parts by mass of the (meth) acryloyl group-containing monomer (C) containing the (meth) acryloyl group-containing monomer (C) having no functional group capable of reacting with. It is characterized by containing in the range of 1 to 20 parts by mass and containing the blocked isocyanate (A) in the range of 0.1 to 20 parts by mass.
• thermosetting composition of the present invention and the thermosetting inkjet ink use blocked isocyanate (A) as a thermosetting agent.
• the blocking agent of the blocked isocyanate (A) is removed by heating at a high temperature, for example, 110 to 180 ° C. for 10 to 60 minutes, so that thermosetting starts.
• the blocking agent is removed from the temperature of about 80 ° C., which is lower than the above temperature, and the reaction proceeds little by little, and as a result, there is a problem that the viscosity increases.
• Increasing the dissociation temperature of the blocking agent will improve this problem, but it will result in insufficient thermosetting.
• the blocked isocyanate (A) having a dissociation temperature within the above temperature range with the compound (B) having a functional group capable of hydrogen bonding with the blocked isocyanate, storage stability and curing at a high temperature are achieved. It succeeded in achieving both sex.
• the compound (B) having a possible functional group is contained in an amount of 0.1 to 20 parts by mass, and the blocked isocyanate (A) is contained in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the (meth) acryloyl group-containing monomer (C).
• the problem of deterioration of the curability of the film surface is solved.
• a photopolymerization initiator in combination, it is preferable to further use a photopolymerization initiator in combination.
• a photopolymerization initiator in combination, the degree of polymerization of the cured film can be increased, and further, the curability of the surface of the cured film under high temperature and high humidity can be improved. This is because the (meth) acryloyl group-containing monomer (C) has a relatively low molecular weight blocked isocyanate (A) and the compound (B) in the cured film due to the increase in viscosity in the film when the polymerization proceeds by irradiation with light.
• the blocking agent of the blocked isocyanate (A) is released during heat curing as described above, the isocyanate group reacts with the compound (B), and the compound (B) is mainly composed of a hydrocarbon group R'. It is presumed that this is because the site is projected to the outside of the molecule and easily oriented to the surface of the cured film, so that the hydrophobicity of the surface of the cured film is further increased.
• a gelling agent it is preferable to have a gelling agent.
• the hydrophobicity of the cured film is increased, it is estimated that the surface of the cured film is also excellent in thermosetting property under high temperature and high humidity.
• thermosetting composition Details of thermosetting composition >> Hereinafter, the structure and the like of the thermosetting composition of the present invention will be described in detail.
• a blocked isocyanate (A) having an isocyanate group protected by a heat-dissociating blocking agent is used.
• a blocked isocyanate (A) in the thermosetting composition the storage stability at high temperature can be improved.
• a polyfunctional isocyanate having two or more isocyanate groups in the molecule is preferable.
• the polyfunctional isocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule.
• 2,4'-Diphenylmethane diisocyanate (2,4'-MDI) 1,4-phenylenediocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), trizine diisocyanate (TODI), 1,5- Aromatic polyisocyanates such as naphthalenediocyanate (NDI); aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornandiisosocyanatemethyl (NBDI); transcyclohexane-1, Alicyclic polyis
• any one of these isocyanates may be used alone or two or more of them may be used.
• blocking agent A known blocking agent can be used.
• alcohols such as ethanol, n-propanol, isopropanol, t-butanol, isobutanol
• phenols such as phenol, chlorphenol, cresol, xylenol, p-nitrophenol, pt-butylphenol, p-sec-butylphenol.
• P-sec-aminophenol, p-octylphenol alkylphenols such as p-nonylphenol, basic nitrogen-containing compounds such as 3-hydroxypyridine, 8-hydroxyquinoline, 8-hydroxyquinaldine, diethyl malonate, ethyl acetoacetate.
• Active methylene compounds such as acetylacetone, acidamides such as acetamido, acrylamide, acetanylide, acidimides such as succinimide and maleateimide, imidazoles such as 2-ethylimidazole and 2-ethyl-4-methylimidazole, Pyrazoles such as pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, lactams such as 2-pyrrolidone and ⁇ -caprolactam, and ketone or aldehyde oximes such as acetoxime, methylethylketone oxime, cyclohexanone oxime and acetoaldoxime. Examples include ethyleneimine and phenolite sulfate.
• the thermally dissociable blocking agent is preferably at least one compound selected from the group consisting of an oxime compound, a pyrazole compound and an active ethylene compound in terms of ink storage stability and thermal dissociation.
• the oxime compound include formamide oxime, acetoaldoxime, acetooxime, methylethylketone oxime, cyclohexanone oxime and the like.
• pyrazole-based compound examples include pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, and the like.
• Examples of the active ethylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, and the like.
• Examples of the polyfunctional isocyanate compound having an isocyanate group protected by the blocking agent include 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate and 2-[(3-butylidene) aminooxycarbonylamino]. Examples thereof include ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl acrylate, and 2-[(3-butylidene) aminooxycarbonylamino] ethyl acrylate.
• the content of the blocked isocyanate (A) 0.1 to 20 parts by mass of the blocked isocyanate (A) is contained with respect to 100 parts by mass of the (meth) acryloyl group-containing monomer (C), and 1 to 10 parts by mass of the blocked isocyanate (A) is contained. It is more preferable that it is included within the range. If (A) is less than 0.1 parts by mass, curing is insufficient by heat, and if more than 20 parts by mass, the thermosetting composition and the heat-consisting inkjet ink have good storage stability at high temperatures. descend.
• one type may be used alone, two or more types may be used in combination, or a plurality of types of blocked isocyanates blocked by one type or two or more types of blocking agents may be used.
• blocked isocyanates include, for example, BI7691 and BI9792 (all manufactured by Baxenden), MF-K60X (manufactured by Asahi Kasei Chemicals), VPLS2253, BL4265SN (all manufactured by Sumika Bayer Urethane) and the like. Can be mentioned.
• the "functional group capable of hydrogen bonding with the blocked isocyanate” in the present invention is a functional group having active hydrogen, and examples thereof include a hydroxy group, a carboxy group, an amino group and a mercapto group.
• hydroxy group alcohols of C1 to C18, phenols, and (meth) acrylate having a hydroxy group are preferable. Specific examples thereof include phenol, p-cresol, ethyl salicylate, ethyl p-hydroxybenzoate, propylene glycol, propylene glycol monomethyl ether and the like.
• carboxy group C1 to C18 aliphatic carboxylic acids and aromatic carboxylic acids are preferable. Specific examples include benzoic acid and the like.
• a primary amine and a secondary amine are preferable, and examples thereof include C1 to C18 aliphatic amines and aromatic amines. Specific examples thereof include aniline and acetanilide.
• C1 to C18 aliphatic mercaptans and aromatic mercaptans are preferable, and specific examples thereof include 1-butanethiol and thiophenol.
• the compound (B) is a monomer containing a (meth) acryloyl group.
• the monomer having a (meth) acryloyl group is preferably an acrylate.
• Examples of monofunctional (meth) acrylates having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 1-methyl-2-hydroxyethyl (meth) acrylate. , 2-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate , (Meta) acrylate 4-hydroxymethylcyclohexylmethyl, (meth) acrylate p-hydroxymethylphenylmethyl, (meth) acrylate 2- (hydroxyethoxy) ethyl, (meth) acrylate 2- (hydroxyethoxyethoxy) Ethyl, 2- (hydroxyethoxyethoxyethoxy) ethyl (meth) acrylate, methyl ⁇ -hydroxymethylacrylate,
• polyfunctional (meth) acrylates having a hydroxy group examples include 2-hydroxy-3-acryloyloxypropyl methacrylate, dipentaerythritol penta (meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) acrylate, and tri.
• Methylolpropandiacrylate glycerin di (meth) acrylate, glycerin acrylate methacrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, hydroxypivalaldehyde-modified di.
• the compound (B) is preferably a compound represented by the following general formula (1) or a polyfunctional acrylate having a hydroxy group. ..
• the organic residue represented by R 4 is a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, and oxygen is formed by an ether bond and / or an ester bond in the structure. It is preferably an alkylene group having 2 to 20 carbon atoms having an atom and an optionally substituted aromatic group having 6 to 11 carbon atoms. Among these, a linear, branched or cyclic alkylene group having 2 to 6 carbon atoms and an alkylene group having 2 to 9 carbon atoms having an oxygen atom by an ether bond in the structure are preferable.
• Specific examples of the compound (B) represented by the general formula (1) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 1-methyl-2 (meth) acrylate. -Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6 (meth) acrylate -Hydroxyhexyl, 4-hydroxymethylcyclohexylmethyl (meth) acrylate, p-hydroxymethylphenylmethyl (meth) acrylate, 2- (hydroxyethoxy) ethyl (meth) acrylate, 2- (hydroxy) (meth) acrylate Ethoxyethoxy) ethyl, 2- (hydroxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2-hydroxy-3-phenoxyprop
• compound (B) More preferred specific examples of compound (B) include 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-, from the viewpoint of curing rate. It contains alicyclic carboxylic acid-based epoxy acrylates such as hydroxy-3-phenoxypropyl acrylate or pentaerythritol triacrylate and acrylic modified products of hexahydrodiphthalic acid glycidyl diester, and dipentaerythritol pentaacrylate, among which pentaerythritol triacrylate. Acrylate is preferred.
• Examples of the (meth) acryloyl group-containing monomer having a carboxy group include acrylic acid, methacrylic acid and the like.
• the blocked isocyanate (A) is contained in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acryloyl group-containing monomer (C). It is more preferable that it is contained in the range of about 10 parts by mass.
• the content of the compound (B) is less than 0.1 parts by mass, the storage stability at high temperature is poor, and when the content is more than 20 parts by mass, the thermosetting composition and the heat-consisting inkjet ink The curability of the cured film under high temperature and high humidity is reduced.
• the (meth) acryloyl group-containing monomer (C) having no functional group capable of reacting with the blocked isocyanate has one or more (meth) acryloyl groups in one molecule.
• the (meth) acryloyl group-containing monomer is a compound having no functional group capable of reacting with isocyanate.
• the functional groups capable of reacting with isocyanate have already been described in compound (B).
• the (meth) acrylate used in the present invention is, for example, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, butyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate.
• the gelling agent according to the present invention is preferably held in a state of being uniformly dispersed in the cured film cured by light and heat, whereby the permeation of water into the cured film can be prevented.
• a gelling agent is a compound of at least one of the compounds represented by the following general formula (G1) or (G2), which is dispersed in the cured film without impairing the curability of the ink. It is preferable in that respect. Further, in inkjet printing, it is preferable in that the pinning property is good, the drawing can be performed with both the fine line and the film thickness, and the fine line reproducibility is excellent.
• General formula (G2): R 3- COO-R 4 (In the equation, R 1 to R 4 each independently represent an alkyl chain having a linear moiety having 12 or more carbon atoms and which may have a branch.)
• the ketone wax represented by the general formula (G1) or the ester wax represented by the general formula (G2) has a linear or branched hydrocarbon group (alkyl chain) having 12 or more carbon atoms. Therefore, the crystallinity of the gelling agent is further enhanced, the water resistance is improved, and a more sufficient space is generated in the following card house structure. Therefore, the ink medium such as the solvent and the photopolymerizable compound is easily encapsulated in the space, and the pinning property of the ink is further improved.
• the number of carbon atoms of the linear or branched hydrocarbon group (alkyl chain) is preferably 26 or less, and when it is 26 or less, the melting point of the gelling agent does not rise excessively, so that the ink is ejected. There is no need to overheat the ink when doing so.
• R 1 and R 2 , or R 3 and R 4 are linear hydrocarbon groups having 12 or more and 23 or less carbon atoms.
• R 1 or R 2 or carbon in which either R 3 or R 4 is saturated is saturated. It is preferably a hydrocarbon group having 12 or more and 23 or less atoms. From the above viewpoint , it is more preferable that both R 1 and R 2 or both R 3 and R 4 are saturated hydrocarbon groups having 11 or more and less than 23 carbon atoms.
• Examples of the ketone wax represented by the general formula (G1) include dilignoceryl ketone (C24-C24), dibehenyl ketone (C22-C22), distearyl ketone (C18-C18), and diicosyl ketone (diicosyl ketone).
• C20-C20 Dipalmitylketone (C16-C16), Dimyristylketone (C14-C14), Dilaurylketone (C12-C12), Laurylmyristylketone (C12-C14), Laurylpalmitylketone (C12-C16) ), Myristyl palmityl ketone (C14-C16), Myristyl stearyl ketone (C14-C18), Myristyl behenyl ketone (C14-C22), Palmityl behenyl ketone (C16-C18), Balmityl behenyl ketone (C16-C22), Stearyl behenyl ketone (C18-C22) is included.
• the carbon number in parentheses represents the carbon number of each of the two hydrocarbon groups separated by the carbonyl group.
• Examples of commercially available ketone waxes represented by the general formula (G1) include Stearone (manufactured by Alfa Aeser; Stearon), 18-Pentriacontane (manufactured by Alfa Aeser), and Hentriacontane-16-on (manufactured by Alfa Aeser). And Kao Wax T-1 (manufactured by Kao Corporation) are included.
• fatty acids or ester waxes represented by the general formula (G2) include behenyl behenylate (C21-C22), icosyl icosanate (C19-C20), stearyl stearate (C17-C18), palmityl stearate (C17).
• ester wax products represented by the general formula (G2) examples include Unistar M-2222SL and Spalm Aceti, manufactured by Nichiyu Co., Ltd. (“Unistar” is a registered trademark of the company), Exepearl SS and Exepearl MY-M, and Kao. Manufactured by the company (“Exepearl” is a registered trademark of the company), EMALEX CC-18 and EMALX CC-10, manufactured by Nippon Emulsion (“EMALEX” is a registered trademark of the company), Amrepus PC, manufactured by Higher Alcohol Industry Co., Ltd. (“Amrepus”) Is a registered trademark of the company).
• ketone wax, ester wax, higher fatty acid, higher alcohol and fatty acid amide are preferable from the viewpoint of further enhancing pinning property.
• the content of the gelling agent according to the present invention is preferably in the range of 0.5 to 5.0% by mass with respect to the total mass of the ink.
• the content of the gelling agent is within the above range, the solubility and pinning effect of the gelling agent on the solvent component are improved, and the water resistance of the cured film is improved.
• the content of the gelling agent in the inkjet ink is more preferably in the range of 0.5 to 2.5% by mass.
• the gelling agent crystallizes in the ink at a temperature equal to or lower than the gelation temperature of the ink.
• the gelling temperature is a temperature at which the gelling agent undergoes a phase transition from the sol to the gel when the solified or liquefied ink is cooled by heating, and the viscosity of the ink suddenly changes.
• the solified or liquefied ink is cooled while measuring the viscosity with a viscoelasticity measuring device (for example, MCR300, manufactured by Physica), and the temperature at which the viscosity rises sharply is set to the temperature of the ink. It can be the gelation temperature.
• the photopolymerization initiator according to the present invention uses a photoradical initiator when the photopolymerizable compound is a radically polymerizable compound, and generates photoacid when the photopolymerizable compound is a cationically polymerizable compound. It is preferable to use an agent.
• thermosetting inkjet ink of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiator.
• the photopolymerization initiator may be a combination of both a photoradical initiator and a photoacid generator.
• Photoradical initiators include cleaved radical initiators and hydrogen abstraction type radical initiators.
• cleaved radical initiators examples include acetophenone-based initiators, benzoin-based initiators, acylphosphine oxide-based initiators, benzyl and methylphenylglioxyesters.
• acetophenone-based initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-.
• Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) Includes propane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone.
• benzoin-based initiators examples include benzoin, benzoin methyl ether and benzoin isopropyl ether.
• acylphosphine oxide-based initiators examples include 2,4,6-trimethylbenzoindiphenylphosphine oxide.
• hydrogen abstractive radical initiators include benzophenone-based initiators, thioxanthone-based initiators, aminobenzophenone-based initiators, 10-butyl-2-chloroacrydone, 2-ethylanthraquinone, 9,10-. Includes phenance radical quinones and camphorquinones.
• benzophenone-based initiators include benzophenone, methyl-4-phenylbenzophenone o-benzoyl benzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, and acrylicized benzophenone. , 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 3,3'-dimethyl-4-methoxybenzophenone.
• thioxanthone-based initiators examples include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone.
• aminobenzophenone-based initiators include Michler ketone and 4,4'-diethylaminobenzophenone.
• photoacid generators examples include the compounds described in Organic Electronics Materials Study Group, "Organic Materials for Imaging", Bunshin Publishing (1993), pp. 187-192.
• the content of the photopolymerization initiator may be within a range in which the ink can be sufficiently cured.
• the content of the photopolymerization initiator is 0, based on the total mass of the thermosetting inkjet ink of the present invention (hereinafter, also simply referred to as the ink of the present invention). It can be in the range of 01 to 10% by mass.
• photopolymerization initiators examples include Irgure TPO (manufactured by BASF), 819 (manufactured by BASF), Irgacure 379 (manufactured by BASF), Genocure ITX (manufactured by Rahn AG) Genocure EPD (Rahn). (A.G.) and the like are included.
• the ink of the present invention may further contain a photopolymerization initiator auxiliary agent, a polymerization inhibitor and the like, if necessary.
• the photopolymerization initiator auxiliary agent may be a tertiary amine compound, and an aromatic tertiary amine compound is preferable.
• aromatic tertiary amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethylamino-p-benzoic acid ethyl ester, Includes N, N-dimethylamino-p-benzoic acid isoamylethyl ester, N, N-dihydroxyethylaniline, triethylamine, N, N-dimethylhexylamine and the like.
• N, N-dimethylamino-p-benzoic acid ethyl ester and N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferable. These compounds may be used alone or in combination of two or more.
• the ink of the present invention may further contain a colorant, if necessary.
• the colorant may be a dye or a pigment, but a pigment is preferable because it has good dispersibility with respect to the constituent components of the ink and is excellent in weather resistance.
• the pigment is not particularly limited, and examples thereof include organic pigments or inorganic pigments having the following numbers listed in the color index.
• red or magenta pigments examples include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53. 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 , 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment A pigment selected from Orange 13, 16, 20, 36 or a mixture thereof is included.
• blue or cyan pigments examples include Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17-1, 22, 27, 28, 29, 36. , 60 pigments selected from, or mixtures thereof and the like.
• green pigments examples include pigments selected from Pigment Green 7, 26, 36, 50 or mixtures thereof.
• yellow pigments examples include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137. 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193, and the like are included.
• black pigments examples include pigments selected from Pigment Black 7, 28, 26 or mixtures thereof.
• Examples of commercially available pigments include Black Pigment (manufactured by Mikuni), Chromofine Yellow 2080, 5900, 5930, AF-1300, 2700L, Chromofine Orange 3700L, 6730, Chromofine Scarlet 6750, Chromofine Magenta 6880, 6886.
• the pigment can be dispersed by, for example, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, or the like.
• the dispersion of the pigment is such that the volume average particle size of the pigment particles is preferably in the range of 0.08 to 0.5 ⁇ m, the maximum particle size is preferably in the range of 0.3 to 10 ⁇ m, and more preferably 0.3 to 3 ⁇ m. It is preferable that the operation is performed so as to be within the range of.
• the dispersion of the pigment is adjusted by the selection of the pigment, the dispersant, and the dispersion medium, the dispersion conditions, the filtration conditions, and the like.
• the ink of the present invention may further contain a dispersant in order to enhance the dispersibility of the pigment.
• a dispersant include hydroxy group carboxylic acid esters, long-chain polyaminoamides and high-molecular-weight acid esters salts, high-molecular-weight polycarboxylic acid salts, long-chain polyaminoamides and polar acid esters salts, and high-molecular-weight unsaturateds.
• Acid ester polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate, Polyoxyethylene nonylphenyl ether, stearylamine acetate and the like are included.
• examples of commercially available dispersants include Avecia's Solspace series and Ajinomoto Fine-Techno's PB series.
• the ink of the present invention may further contain a dispersion aid, if necessary.
• the dispersion aid may be selected according to the pigment.
• the total amount of the dispersant and the dispersion aid is preferably in the range of 1 to 50% by mass with respect to the pigment.
• the ink of the present invention may further contain a dispersion medium for dispersing the pigment, if necessary.
• a solvent may be contained in the ink as a dispersion medium, but in order to suppress the residue of the solvent in the formed image, the above-mentioned photopolymerizable compound (particularly a monomer having a low viscosity) is used as the dispersion medium. Is preferable.
• dyes examples include oil-soluble dyes.
• oil-soluble dyes include the following various dyes.
• magenta dyes include MS Magenta VP, MS Magenta HM-1450, MS Magenta HSo-147 (above, manufactured by Mitsui Chemical Co., Ltd.), AIZENSOT Red-1, AIZEN SOT Red-2, AIZEN SOTRed-3, AIZEN SOT.
• cyan dyes examples include MS Cyan HM-1238, MS Cyan HSo-16, Cyan HSo-144, MS Cyan VPG (above, manufactured by Mitsui Chemical Co., Ltd.), AIZEN SOT Blue-4 (manufactured by Hodogaya Chemical Co., Ltd.), and RESOLIN.
• BR Blue BGLN 200%, MACROLEX Blue RR, CERES Blue GN, SIRIUS SUPRATURQ. Blue Z-BGL, SIRIUS SUPRA TURQ.
• Blue FB-LL 330% aboveve, manufactured by Bayer Japan
• KAYASET Blue FR KAYASET Blue N
• KAYASET Blue 814 Turq.
• Blue GL-5 200 Light Blue BGL-5200 (above, manufactured by Nippon Kayaku Co., Ltd.), DAIWA Blue 7000, OleosolFast Blue GL (above, manufactured by Daiwa Kasei Co., Ltd.), DIARESIN Blue P (manufactured by Mitsubishi Kayaku Co., Ltd.), SUDA , NEOPEN Blue 808, ZAPON Blue 806 (above, manufactured by BASF Japan Ltd.) and the like are included.
• yellow dyes examples include MS Yellow HSm-41, Yellow KX-7, Yellow EX-27 (above, manufactured by Mitsui Kagaku Co., Ltd.), AIZEN SOT Yellow-1, AIZEN SOT Yellow-6, AIZEN SOT Yellow-6 (above). , Hodogaya Chemical Co., Ltd.), MACROLEX Yellow 6G, MACROLEX FLUOR.
• black dyes examples include MS Black VPC (manufactured by Mitsui Chemicals), AIZEN SOT Black-1, AIZEN SOT Black-5 (above, manufactured by Hodogaya Chemical Co., Ltd.), RESORIN Black GSN 200%, RESOLIN BlackBS (above, Bayer). Japan), KAYASET Black AN (Nippon Kayaku), DAIWA Black MSC (Daiwa Kasei), HSB-202 (Mitsubishi Kasei), NEPTUNE Black X60, NEOPEN Black X58 (above, BASF Japan) (Made by company) etc. are included.
• the colorant may contain one or more of the colorants in the ink of the present invention and may be toned to a desired color.
• the content of the colorant is preferably in the range of 0.1 to 20% by mass, and more preferably in the range of 0.4 to 10% by mass with respect to the total amount of the ink.
• the ink of the present invention may further contain other components including a polymerization inhibitor and a surfactant as long as the effects of the present invention can be obtained. Only one kind of these components may be contained in the ink of the present invention, or two or more kinds may be contained in the ink.
• anti-polymerization agents examples include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiline, p-benzoquinone.
• polymerization inhibitors examples include Irgastab UV10 (manufactured by BASF), Genorad 18 (manufactured by Rahn AG), and the like.
• the amount of the polymerization inhibitor can be arbitrarily set within the range in which the effect of the present invention can be obtained.
• the amount of the polymerization inhibitor can be, for example, 0.001% by mass or more and less than 1.0% by mass with respect to the total mass of the ink.
• surfactants examples include anionic surfactants such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates and fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols and polyoxy. Includes nonionic surfactants such as ethylene / polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and silicone-based and fluorine-based surfactants.
• anionic surfactants such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates and fatty acid salts
• nonionic surfactants such as ethylene / polyoxypropylene block copolymers
• cationic surfactants such as alkylamine salts and quaternary ammonium salts
• silicone-based and fluorine-based surfactants examples include silicone-
• silicone-based surfactants include polyether-modified polysiloxane compounds, specifically Tego rad 2250, manufactured by Evonik, KF-351A, KF-352A, KF-642 and X-22-4272, Shin-Etsu. Included are Chemical Industries, BYK307, BYK345, BYK347 and BYK348, Big Chemie (“BYK” is a registered trademark of the company), and TSF4452, Momentive Performance Materials.
• polyether-modified polysiloxane compounds specifically Tego rad 2250, manufactured by Evonik, KF-351A, KF-352A, KF-642 and X-22-4272, Shin-Etsu. Included are Chemical Industries, BYK307, BYK345, BYK347 and BYK348, Big Chemie (“BYK” is a registered trademark of the company), and TSF4452, Momentive Performance Materials.
• the fluorine-based surfactant means a surfactant in which a part or all of the hydrogen is substituted with hydrogen instead of hydrogen bonded to the carbon of the hydrophobic group of the ordinary surfactant.
• fluorine-based surfactants are Megafac F, DIC (“Megafac” is a registered trademark of the company), Surflon, AGC Seichemical (“Surflon” is a registered trademark of the company), Flurad FC, 3M. (“Fluorad” is a registered trademark of the company), Monflor, Imperial Chemical Industry, Zonyls, E.I. , Made by Neos (“FTERGENT” is a registered trademark of the company).
• the amount of the surfactant can be arbitrarily set within the range in which the effect of the present invention can be obtained.
• the amount of the surfactant can be, for example, 0.001% by mass or more and less than 1.0% by mass with respect to the total mass of the ink.
• a curing accelerator may be contained if necessary.
• the curing accelerator can be used without particular limitation as long as it promotes the thermal curing of the resin component.
• Examples of curing accelerators include imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-tetraphenylborate, 1,8-diazabicyclo [5.4]. .0] Undecene-7-tetraphenylborate and the like can be mentioned.
• coupling agent In the present invention, various coupling agents may be included if necessary. By including the coupling agent, the adhesion with the copper foil can be improved. Examples of various coupling agents include silane-based, titanium-based, and aluminum-based coupling agents.
• an ion scavenger may be contained if necessary.
• the inclusion of the ion scavenger has an advantage that ionic impurities are adsorbed and the insulating property under the condition that the cured film absorbs moisture is improved.
• ion scavenger examples include inorganic ion adsorbents such as triazine thiol compounds, bisphenol-based reducing agents, zirconium compounds, and antimony bismas-based magnesium aluminum compounds.
• solvent-free is originally preferable from the viewpoint of curability, but it can also be added for adjusting the ink viscosity.
• the ink of the present invention preferably contains a gelling agent.
• the viscosity of the ink of the present invention at 25 ° C. is in the range of 1 to 1 ⁇ 10 4 Pa ⁇ s, so that the ink is sufficiently gelled when it lands and the temperature is lowered to room temperature, and pinning property is obtained. Is preferable in that
• the viscosity of the ink of the present invention at 80 ° C. is preferably in the range of 3 to 20 mPa ⁇ s, and is in the range of 7 to 9 mPa ⁇ s. Is more preferable.
• the ink of the present invention contains a gelling agent
• it is preferable that the ink has a phase transition point in the range of 40 ° C. or higher and lower than 100 ° C.
• the phase transition point is 40 ° C. or higher, the ink rapidly gels after landing on the recording medium, so that the pinning property becomes higher. Further, when the phase transition point is less than 100 ° C., the ink handling property becomes good and the injection stability becomes high.
• the phase transition point of the ink of the present invention is more preferably in the range of 40 to 60 ° C.
• the viscosity of the ink of the present invention at 80 ° C., the viscosity at 25 ° C., and the phase transition point can be determined by measuring the temperature change of the dynamic viscoelasticity of the ink with a rheometer.
• these viscosities and phase transition points are values obtained by the following methods.
• the ink of the present invention is heated to 100 ° C., and while measuring the viscosity with Physica MCR301 (manufactured by Antonio Par) and a shear rate of 1000 (1 / s), the shear rate is 11.7 (1 / s) and the temperature lowering rate is 0.
• the ink is cooled to 20 ° C. under the condition of 1 ° C./s to obtain a temperature change curve of viscosity.
• the viscosity at 80 ° C. and the viscosity at 25 ° C. can be obtained by reading the viscosities at 80 ° C. and 25 ° C. on the temperature change curve of the viscosity, respectively.
• the phase transition point can be determined as the temperature at which the viscosity becomes 200 mPa ⁇ s in the temperature change curve of the viscosity.
• the average dispersed particle size of the pigment particles according to the present invention is preferably in the range of 50 to 150 nm, and the maximum particle size is preferably in the range of 300 to 1000 nm. .. A more preferable average dispersed particle size is in the range of 80 to 130 nm.
• the average dispersed particle size of the pigment particles in the present invention means a value obtained by a dynamic light scattering method using a data sizer nano ZSP manufactured by Malvern. Since the ink containing the colorant has a high density and does not transmit light with this measuring device, the ink is diluted 200 times before measurement.
• the measurement temperature is room temperature (25 ° C).
• thermosetting inkjet ink of the present invention is preferably an ink for forming a solder resist pattern used for a printed circuit board.
• a solder resist pattern solder resist film
• the adhesion at the interface of the resist film is improved, the migration of copper is prevented, and the deterioration of the insulating property can be suppressed.
• the method for forming a solder resist film using the heat-curable inkjet ink of the present invention includes (1) a step of ejecting the ink of the present invention from a nozzle of an inkjet head and landing it on a circuit-formed printed circuit substrate. (3) It is preferable to include a step of heating the ink to perform main curing.
• the landed ink is irradiated with active light during the steps (1) and (3) above to apply the ink. It is preferable to include a step of pre-curing (step (2)).
• Step (1) droplets of the ink of the present invention are ejected from an inkjet head and landed on a printed circuit board, which is a recording medium, at a position corresponding to a resist film to be formed, and patterned.
• the ejection method from the inkjet head may be either an on-demand method or a continuous method.
• On-demand inkjet heads include electro-mechanical conversion methods such as single cavity type, double cavity type, bender type, piston type, shared mode type and shared wall type, as well as thermal inkjet type and bubble jet (registered trademark). (Bubble jet is a registered trademark of Canon Inc.) Any of the electric-heat conversion methods such as the type may be used.
• the ejection stability can be improved by ejecting ink droplets from the inkjet head in a heated state.
• the temperature of the ink at the time of ejection is preferably in the range of 40 to 100 ° C., and more preferably in the range of 40 to 90 ° C. in order to further improve the ejection stability.
• the temperature of the ink when filled in the inkjet head is (gelling temperature +10) ° C. to (gelling).
• the temperature is preferably set to +30) ° C.
• the temperature of the ink in the inkjet head is (gelling temperature +10) ° C. or higher, the ink does not gel in the inkjet head or on the nozzle surface, and the ink ejection property does not deteriorate.
• the temperature of the ink in the inkjet head is within (gelling temperature +30) ° C., the ink does not become too high and the ink component does not deteriorate.
• the method of heating the ink is not particularly limited.
• at least one of the ink tank, the supply pipe, the ink supply system such as the front chamber ink tank immediately before the head, the pipe with a filter, the piezo head, etc., which constitute the head carriage, is heated by a panel heater, a ribbon heater, warm water, or the like. be able to.
• the amount of ink droplets to be ejected is preferably in the range of 2 to 20 pL from the viewpoint of recording speed and image quality.
• the printed circuit board is not particularly limited, but for example, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine / polyethylene / PPO / cyanate ester.
• Step (2) the ink landed in the step (1) is irradiated with active light to temporarily cure the ink.
• the active ray can be selected from, for example, electron beam, ultraviolet ray, ⁇ ray, ⁇ ray, X-ray and the like, but ultraviolet ray is preferable.
• Ultraviolet irradiation can be performed under conditions of a wavelength of 395 nm, for example, using a water-cooled LED manufactured by Phoseon Technology.
• a water-cooled LED manufactured by Phoseon Technology.
• the peak illuminance on the surface of the resist film of ultraviolet rays having a wavelength in the range of 370 to 410 nm is preferably in the range of 0.5 to 10 W / cm 2 , more preferably in the range of 1 to 5 W / cm 2 . Do it so that it is inside.
• the amount of light applied to the resist film is preferably less than 500 mJ / cm 2.
• the irradiation of the active light beam is preferably performed within 0.001 to 300 seconds after the ink lands, and more preferably within 0.001 to 60 seconds in order to form a high-definition resist film.
• Step (3) After the temporary curing of (2), the ink is further heated to be main-cured.
• a heating method for example, it is preferable to put it in an oven set in the range of 110 to 180 ° C. for 10 to 60 minutes.
• thermosetting inkjet ink of the present invention can be used not only as the ink for forming the solder resist pattern described above, but also as an adhesive, a sealing agent, a circuit protective agent, and the like for electronic parts.
• Example 1 [Preparation of Thermosetting Compositions 1-1 to 1-44]
• Ingredients were blended and stirred with a dissolver to give thermosetting compositions 1-1 to 1-44.
• thermosetting compositions 1-45 to 1-58 Thermosetting by combining each component of the compound (B) having a functional group capable of hydrogen bonding with the blocked isocyanate (A) and the (meth) acryloyl group-containing monomer (C) having no functional group capable of reacting with the blocked isocyanate. It was 96% by mass of the total composition. The addition amount ratio is shown in Table III. Furthermore, the photopolymerization initiator and the photopolymerization initiator auxiliary agent are blended in the following amounts, respectively. This was stirred with a dissolver to obtain thermosetting compositions 1-45 to 1-58. Photopolymerization initiator Irgacure TPO (manufactured by BASF): 1.0% by mass Photopolymerization Initiator Genocure ITX (manufactured by Rahn AG): 3.0% by mass
• thermosetting compositions 1 to 58 Using these thermosetting compositions 1 to 58, a film having a thickness of 30 ⁇ m was formed on a BT substrate using an applicator (manufactured by ERICHSEN), and the thermosetting compositions 1-1 to 1-44 were formed. It was cured at 160 ° C. for 30 minutes to form cured films 1-1 to 1-44. Further, for the thermosetting compositions 1-45 to 1-58, the film was cured by irradiating an LED lamp (395 nm, 8 W / cm 2 , water cooled unit) manufactured by Phoseon Technology Co., Ltd. to 500 mJ / cm 2. Then, it was cured at 160 degrees for 30 minutes to form a cured film 1-45 to 1-58.
• an LED lamp 395 nm, 8 W / cm 2 , water cooled unit
• A-1 Trixene BI7691 (manufactured by LANXESS, biuret type, blocking agent: DMP (dimethylpyrazole))
• A-2 Trixene BI7982 (manufactured by LANXESS, blocking agent: DMP)
• A-3 Trixene BI9792 (manufactured by LANXESS, blocking agent: DMP / DEM (diethyl malonate) active ethylene compound)
• A-4 BL4265SN (manufactured by Sumika Bayer Urethane Co., Ltd., blocking agent: MEKO (methyl ethyl ketooxime) oxime compound)
• A-5 Trixene BI7991 (manufactured by LANXESS, biuret type, blocking agent: DMP / DEM)
• A-6 Death Module BL 1100/1 (manufactured by Sumika Bayer Urethane, blocking agent
• C-1 Dipropylene glycol diacrylate (DPGDA: manufactured by M222 Miwon)
• DPGDA Dipropylene glycol diacrylate
• C-2 TMP (EO) 9TA (trimethylolpropane EO-modified triacrylate) (EM2382 manufactured by Choko Kagaku Co., Ltd.)
• C-3 Phenylglycidyl ether acrylate Hexamethylene diisocyanate urethane prepolymer (Urethane acrylate AH-600: manufactured by Kyoeisha Chemical Co., Ltd.)
• Thickness thickening rate is less than 5% ⁇ : Thickness thickening rate is 5% or more and less than 10 ⁇ : Thickness thickening rate is 10% or more and less than 20
• the wood part of the pencil was scraped off and the core was made 5 to 6 mm long.
• a pencil was used in which the tip of the core was smoothly polished with abrasive paper to obtain a circular cross section. The pencil was held at an angle of 45 degrees with respect to the surface of the sample, and the coating film was scratched at an angle of 45 degrees with a load of 1 kg applied to the surface of the sample. The maximum hardness of the pencil whose coating film did not reach the substrate was evaluated.
• thermosetting property As is clear from the results shown in Tables I to III, the compounds within the scope of the present invention are clear from the materials having excellent storage stability at high temperature, thermosetting property, and thermosetting property at high temperature and high humidity. Is. Further, with respect to 100 parts by mass of the (meth) acryloyl group-containing monomer (C), 1 to 10 parts by mass of the compound (B) having a functional group capable of hydrogen bonding, or 1 to 10 parts by mass of the blocked isocyanate (A). It can be seen that the thermosetting composition obtained is more excellent in ink storage stability.
• the compound (B) having a functional group capable of hydrogen bonding is a (meth) acryloyl group-containing monomer, it is excellent in ink storage stability and pencil hardness. Further, it can be seen that the thermosetting composition irradiated with light using the photopolymerization initiator has excellent pencil hardness.
• Example 2 [Preparation of inkjet ink] ⁇ Preparation of yellow pigment dispersion>
• the following dispersant 1 and dispersant 2 and the dispersion medium are placed in a stainless beaker, heated and dissolved on a hot plate at 65 ° C. for 1 hour, cooled to room temperature, and then the following pigment is added to the diameter. It was placed in a glass bottle together with 200 g of 0.5 mm zirconia beads and sealed tightly. This was dispersed with a paint shaker until the desired particle size was obtained, and then the zirconia beads were removed.
• Dispersant 1 EFKA7701 (manufactured by BASF) 5.6 parts by mass Dispersant 2: Solspace 22000 (manufactured by Japan Lubrizol) 0.4 parts by mass Dispersion medium: Dipropylene glycol diacrylate (containing 0.2% UV-10) 80.6 parts by mass Pigment: PY185 (BASF, Paliotor Yellow D1155) 13.4 parts by mass
• Dispersant EFKA7701 (manufactured by BASF) 7 parts by mass Dispersion medium: Dipropylene glycol diacrylate (containing 0.2% UV-10) 70 parts by mass Pigment: PB15: 4 (manufactured by Dainichiseika, Chromofine Blue 6332JC) 23 parts by mass
• thermosetting inkjet ink Preparation of thermosetting inkjet ink
• Thermosetting inkjet inks are blended according to the composition shown below, mixed with a dissolver to prepare, and filtered through a Teflon (registered trademark) 3 ⁇ m membrane filter manufactured by ADVATEC to perform thermosetting inkjet ink 2-. 1-2-68 were prepared.
• thermosetting inkjet inks 2-1 to 2-41 Blocked isocyanate (A), compound (B) having a functional group capable of hydrogen bonding, and (meth) acryloyl group-containing monomer (C) having no functional group capable of reacting with blocked isocyanate are combined to form 93. It was set to 0 parts by mass. The addition amount ratio is shown in Tables IV and V. Further, the following components were added. -Yellow pigment dispersion: 1.0% by mass -Cyan pigment dispersion: 2.0% by mass -Photopolymerization initiator: TPO: 1.0% by mass -Photopolymerization initiator: ITX: 3.0% by mass
• thermosetting inkjet inks 2-42 to 2-56 Blocked isocyanate (A), compound (B) having a functional group capable of hydrogen bonding, and (meth) acryloyl group-containing monomer (C) having no functional group capable of reacting with blocked isocyanate are combined to form 90. It was set to 0 parts by mass. The addition amount ratio is shown in Tables V and VI. Further, the following components were added.
• thermosetting inkjet inks 2-57 to 2-62 Blocked isocyanate (A), compound (B) having a functional group capable of hydrogen bonding, and (meth) acryloyl group-containing monomer (C) having no functional group capable of reacting with blocked isocyanate are combined to make 97. It was set to 0 parts by mass. The addition amount ratio is shown in Table VI. Further, the following components were added. -Yellow pigment dispersion: 1.0% by mass -Cyan pigment dispersion: 2.0% by mass
• thermosetting inkjet inks 2-63 to 2-68 Blocked isocyanate (A), compound (B) having a functional group capable of hydrogen bonding, and (meth) acryloyl group-containing monomer (C) having no functional group capable of reacting with blocked isocyanate are combined to make 94. It was set to 0 parts by mass. The addition amount ratio is shown in Table VI. Further, the following components were added. -Yellow pigment dispersion: 1.0% by mass -Cyan pigment dispersion: 2.0% by mass -Gelling agent D-1: 2.0% by mass -Gelling agent D-2: 1.0% by mass
• the gel phase transition temperature has a complex viscosity in a viscoelastic curve obtained by changing the temperature at a temperature lowering rate of 0.1 ° C./s, a strain of 5%, an angular frequency of 10 radian / s, and a temperature lowering rate of 0.1 ° C./s. It represents the temperature at which the rate is 1 Pa ⁇ s or more.
• the viscosity of the ink containing the gelling agent of the present invention at 25 ° C. is 1 to 1 ⁇ 10 4 Pa ⁇ s, whereas the ink without the gelling agent is less than 1 Pa ⁇ s. Met.
• the gel phase transition temperature of the ink containing the gelling agent of the present invention was 40 to 100 ° C., but the gel phase transition phenomenon was not observed in the ink containing no gelling agent. ..
• thermosetting inkjet ink Each of the prepared thermosetting inkjet inks was loaded into an inkjet recording apparatus having an inkjet recording head equipped with a piezo type inkjet nozzle. Using this device, a pattern was formed on a copper-clad laminate for a printed wiring board (FR-4 thickness 1.6 mm, size 150 mm ⁇ 95 mm).
• the ink supply system consists of an ink tank, an ink flow path, a sub ink tank immediately before the inkjet recording head, a pipe with a metal filter, and a piezo head.
• the ink is heated to 90 ° C. from the ink tank to the head portion.
• the piezo head also had a built-in heater, and the ink temperature in the recording head was heated to 90 ° C.
• heads having a nozzle diameter of 22 ⁇ m and a nozzle resolution of 360 dpi were arranged in a staggered manner to form a nozzle row of 720 dpi.
• the inkjet device Using this inkjet device, a voltage is applied so that the amount of droplets becomes 6.0 pl dots, and a solid pattern of 20 mm ⁇ 50 mm and a comb-shaped pattern with a line & space of 100 ⁇ m are formed on the substrate, respectively.
• the ink layer After printing to a value of 20 ⁇ m, the ink layer was tentatively cured by irradiating an LED lamp (395 nm, 8 W / cm 2 , water cooled unit) manufactured by Phoseon Technology Co., Ltd. to a value of 500 mJ / cm 2. Then, it was put into an oven set at 150 ° C. for 60 minutes and finally cured to obtain a print sample.
• thermosetting inkjet ink of the present invention is clear as a material having excellent storage stability and heat and photocurability. Further, with respect to 100 parts by mass of the (meth) acryloyl group-containing monomer (C), 1 to 10 parts by mass of the compound (B) having a functional group capable of hydrogen bonding, or 1 to 10 parts by mass of the blocked isocyanate (A). It can be seen that the composition is more excellent in ink storage stability.
• the ink storage stability is further excellent. It is presumed that this is because the structure is such that hydrogen bonds to the blocked site of blocked isocyanate are easy.
• the ink storage stability and the thermosetting property are further improved by adding the gelling agent to the heat and photocurable composition of the present invention.
• thermosetting composition of the present invention is excellent in storage stability at high temperature and thermosetting property of the surface of the cured film under high temperature and high humidity, and can be preferably applied to a thermosetting inkjet ink.

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• 2020
  • 2020-11-02 WO PCT/JP2020/041078 patent/WO2021090809A1/ja not_active Ceased
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