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WO2021200267A1 - Composition durcissable et produit durci associé - Google Patents

Composition durcissable et produit durci associé Download PDF

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Publication number
WO2021200267A1
WO2021200267A1 PCT/JP2021/011345 JP2021011345W WO2021200267A1 WO 2021200267 A1 WO2021200267 A1 WO 2021200267A1 JP 2021011345 W JP2021011345 W JP 2021011345W WO 2021200267 A1 WO2021200267 A1 WO 2021200267A1
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WO
WIPO (PCT)
Prior art keywords
curable composition
cured product
meth
group
acrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/011345
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English (en)
Japanese (ja)
Inventor
横山　裕
脩平 ▲高▼嶋
伊藤　秀之
悠斗 小田桐
一善 米田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyo Holdings Co Ltd
Original Assignee
Taiyo Ink Mfg Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Priority to CN202180023025.1A priority Critical patent/CN115315450B/zh
Priority to KR1020227030910A priority patent/KR20220161284A/ko
Publication of WO2021200267A1 publication Critical patent/WO2021200267A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a curable composition and a cured product thereof, particularly a curable composition suitable for an inkjet printing method, and a cured product thereof which can be applied to a flexible printed wiring board and also has flame retardancy.
  • solder resists are used to protect the conductor circuits on the substrate from adhesion of solder.
  • photodeveloping methods and screen printing methods have been adopted as methods for forming solder resists.
  • screen printing methods have been adopted as methods for forming solder resists.
  • an inkjet printing method capable of directly drawing a predetermined print pattern from digital data is being adopted (Patent Document 1).
  • the curable composition capable of forming the solder resist is easy to spray due to the inkjet printing method (good coatability), and the formed solder resist can cope with the miniaturization of the circuit pattern.
  • Excellent resolution, excellent solder heat resistance, high flame retardancy to cover the low flame retardancy of flexible printed wiring boards, and low warpage for flexible printed wiring board applications (low warpage) Having sex), etc. multiple performances are required at the same time.
  • the coatability, resolution or warpage of the cured product may be deteriorated. It can be said that selection is one of the major issues.
  • Patent Document 1 does not take into consideration the above-mentioned problems. Therefore, the present inventor has provided a curable composition having a plurality of performances at the same time and a cured product thereof (for example, solder resist), which is suitable for a flexible printed wiring board for inkjet printing as described above. The challenge was to find out.
  • a curable composition having a plurality of performances at the same time and a cured product thereof (for example, solder resist), which is suitable for a flexible printed wiring board for inkjet printing as described above. The challenge was to find out.
  • the present inventors mainly conducted compounds having three different (meth) acryloyl groups, and a cyano group (-CN), a hydroxyl group (-OH) and a methyl group.
  • the present invention has been completed by finding that a curable composition containing a phenoxy group substituted with any one of the above and a flame retardant having a phosphazene structure and a cured product thereof can solve the above-mentioned problems.
  • the problem in the present invention is At least the following components (A) to (D):
  • (B) A flame retardant having a phenoxy group and a phosphazene structure substituted with any one of a cyano group (-CN), a hydroxyl group (-OH) and a methyl group. It can be solved by a curable composition containing (C) a photopolymerization initiator and (D) a thermosetting component and having a viscosity of 50 mPa ⁇ s or less at 50 ° C.
  • a preferred embodiment of the present invention relates to a curable composition in which the phenoxy group of the flame retardant (B) is substituted with a cyano group.
  • Another preferred embodiment of the present invention relates to a curable composition used for forming a cured film on a flexible printed wiring board.
  • Yet another aspect of the present invention relates to a cured product obtained from the curable composition, an electronic component having the cured product, particularly a flexible printed wiring board.
  • a curable composition having a coatability suitable for an inkjet printing method is provided, and further, a cured product (cured film) obtained from the curable composition has only excellent flame retardancy. It has good flame retardancy, low warpage, good resolution as a solder resist, and solder heat resistance for flexible printed wiring boards.
  • the curable composition of the present invention is adjusted to a viscosity within the range of 50 Pa ⁇ s or less at 50 ° C. for use in inkjet printing.
  • the viscosity was set to 50 ° C., 100 rpm, and 30 seconds according to the viscosity measurement method using a 10 cone-plate type rotational viscometer of JIS Z8803: 2011, and 1 ° 34'x R24 was used as the cone rotor. It is a value measured by a cone plate type viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.).
  • the viscosity at 50 ° C. is 50 mPa ⁇ s or less, it is suitable as an inkjet printing method.
  • the coatability of the curable composition of the present invention and the excellent flame retardancy, good resolution, solder heat resistance and warpage of the cured product obtained from the curable composition are basically obtained.
  • Three compounds having one, two or three (meth) acryloyl groups in one molecule (A) in the curable composition (hereinafter, also simply referred to as "(A) compound"), And (B) a flame retardant having a phosphazene structure and a phenoxy group substituted with any one of a cyano group (-CN), a hydroxyl group (-OH) and a methyl group (hereinafter, also simply referred to as "(B) flame retardant”). It can be demonstrated by the existence of)).
  • the curable composition is coated on the copper surface of the sulfuric acid-treated Espanex M using an inkjet printing device or the like, and the surface of the coating film is visually observed. This can be done by checking whether it is uniform, whether there are streaks, and whether there are any omissions.
  • the flame retardancy of a cured product obtained from a curable composition is obtained, for example, after the curable composition is applied onto a substrate using an inkjet printing device or the like to form a cured film.
  • the cured film can be evaluated by performing a thin vertical combustion test according to the UL94 standard.
  • the curable composition is applied onto the copper surface of the sulfuric acid-treated Espanex M using an inkjet printing device or the like to form an opening shape (cross section) of the cured film.
  • the shape) can be evaluated by observing whether or not the wall surface of the opening is missing or bleeding, and whether or not it is circular.
  • a curable composition is applied onto a polyimide substrate which has been subjected to sulfuric acid treatment and copper plating using an inkjet printing device or the like to obtain a cured film, and then a flux is applied. This can be done by immersing in a solder bath at about 260 ° C., flux cleaning, and then checking for swelling or peeling of the cured film by tape peeling.
  • the warpage of the cured product is determined by, for example, applying a curable composition to a polyimide substrate using an inkjet printing device or the like to obtain a cured film, cutting it into squares, and measuring the degree of warpage of the four corners. Can be evaluated by
  • the three compounds having one, two or three (meth) acryloyl groups in one molecule are the compounds having one (meth) acryloyl group in one molecule, and one molecule. It refers to a combination of three compounds having two (meth) acryloyl groups in one molecule and a compound having three (meth) acryloyl groups in one molecule, or a mixture of these three compounds.
  • a curable composition having a coatability suitable for the in-jet printing method can be obtained, and after the curing, it can be applied to a flexible printed wiring board.
  • a cured product having matching flame retardancy, resolution, solder heat resistance and low warpage can be obtained.
  • Examples of the compound having one (meth) acryloyl group in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 4-hydroxybutyl ( An aliphatic (meth) acrylate such as meth) acrylate, hydroxypropyl (meth) acrylate, butoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, and glycerol mono (meth) acrylate.
  • Acrylate type (meth) acrylate such as acrylate, cyclohexyl (meth) acrylate, 4- (meth) acryloxitricyclo [5.2.1.02,6] decane, isobornyl (meth) acrylate, phenoxyethyl (meth) ) Acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, aromatic (meth) acrylate such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, aliphatic epoxy-modified (meth) acrylate-modified (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloxyalkyl phosphate, 2- (meth) acryloyloxyethyl phosphate, (meth) acryloyloxyethyl phthalic acid, ⁇ - (meth) acryloxyalkyltri Acrylate silane and the like
  • Examples of the compound having two (meth) acryloyl groups in one molecule include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and 1,10.
  • diols such as decanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, Polypropylene glycol diacrylate, neopentyl glycol diacrylate, diacrylate of diol obtained by adding at least one of ethylene oxide and propylene oxide to neopentyl glycol, glycol such as caprolactone-modified hydroxypivalate neopentyl glycol diacrylate Diacrylate, bisphenol A EO adduct diacrylate, bisphenol A PO adduct diacrylate, tricyclodecanedimethanol diacrylate, hydrogenated dicyclopentadienyl diacrylate, cyclohexyl diacrylate and other diacrylates having a cyclic structure. And so on.
  • Examples of the compound having three (meth) acryloyl groups in one molecule include trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane PO-modified triacrylate, and trimethylolpropane EO-modified triacrylate, trifunctional polyester. Acrylate and the like can be mentioned.
  • the compound (A) contains a compound having an aromatic ring and two or three (meth) acryloyl groups.
  • Compounds having an aromatic ring and having two or three (meth) acryloyl groups include, for example, polyhydric phenol (meth) acrylates and alkylene oxide adducts thereof.
  • polyhydric phenol examples include bisphenols such as bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol PH, and bisphenol Z, and biphenol.
  • alkylene oxide examples include ethylene oxide, propylene oxide, and butylene oxide. The number of alkylene oxides added is preferably 6 or less.
  • the compound (A) as described above is contained in the curable composition as a whole in an amount such that the curable composition can maintain a viscosity suitable for inkjet printing.
  • the content of the compound (A) in the curable composition is preferably, for example, approximately 30 parts by mass to 90 parts by mass with respect to 100 parts by mass of the curable composition. Within the numerical range, the viscosity of the curable composition can be maintained at 50 mPa ⁇ s or less at 50 ° C.
  • the flame retardant may be blended for the purpose of imparting flame retardancy to the cured product obtained after curing of the curable composition.
  • the flame retardant (B) used in the present invention has an advantage that the flame retardancy of the cured product can be enhanced without impairing the coatability, resolution or warpage of the cured product.
  • the flame retardant (B) used in the present invention has a hexaphenoxycyclotriphosphazene structure as a basic skeleton, and at least two of the six phenoxy groups in the structure are cyano groups (-CN) or hydroxyl groups (-CN). It is preferably substituted with ⁇ OH).
  • only one of the two phenoxy groups attached to the phosphorus atom in the hexaphenoxycyclotriphosphazene structure is substituted with and thus substituted with one cyano group (-CN). It is a structure having two hexaphenoxycyclotriphosphazene structures as a whole.
  • the two phenoxy groups attached to the phosphorus atom in the hexaphenoxycyclotriphosphazene structure are both substituted with one cyano group (-CN), and the phenoxy group thus substituted.
  • -CN cyano group
  • only one of the two phenoxy groups attached to the phosphorus atom in the hexaphenoxycyclotriphosphazene structure is substituted with one hydroxyl group (-OH) and thus thus. It is a structure having three substituted phenoxy groups as a whole hexaphenoxycyclotriphosphazene structure.
  • the flame retardant (B) in the present invention has the following structure: or or It has one of the above structures.
  • Examples of the preferred (B) commercially available flame retardant include FP-300B, FP-300, and SPH-100 (all manufactured by Fushimi Pharmaceutical Co., Ltd.).
  • the content of the flame retardant (B) is preferably determined based on the amount of the compound (A) as described above, and may be contained in an amount of 1 to 60 parts by mass with respect to 100 parts by mass of the total amount of the compound (A). Preferably, 5 to 40 parts by mass is more preferable.
  • the (C) photopolymerization initiator may be any one capable of polymerizing the (A) compound by irradiation with energy rays such as ultraviolet rays, electron beams, and chemical rays.
  • energy rays such as ultraviolet rays, electron beams, and chemical rays.
  • Examples of the photopolymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2.
  • -Acetophenones such as diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethyl Aminoacetophenones such as amino-1- (4-morpholinophenyl) -butane-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloro Anthraquinones such as anthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal
  • Omnirad 907 examples of commercially available products include Omnirad 907, Omnirad 127, Omnirad 379 (all manufactured by IGM Resins) and the like.
  • the content of the photopolymerization initiator (C) is preferably 0.2 parts by mass to 25 parts by mass, more preferably 0.5 parts by mass to 20 parts by mass, based on 100 parts by mass of the curable composition of the present invention. preferable. When it is in the range of 0.2 to 25 parts by mass, the surface curability of the cured product is good.
  • the curable composition of the present invention may contain (D) a thermosetting component.
  • a thermosetting component examples include those usually used in the art, and for example, known compounds such as blocked isocyanate compounds, epoxy compounds, and oxetane compounds can be used.
  • a latent thermosetting component in which the functional group in the structure is protected by a protecting group can be preferably used.
  • the protecting group can be easily removed by heating or the like when a reaction is desired.
  • the potential means a property that does not show activity at room temperature or a little heating condition, but is activated by heating at a high temperature of 80 ° C. or higher and shows thermosetting property.
  • the latent thermosetting component is preferably a blocked isocyanate compound.
  • the blocked isocyanate compound is preferably a compound having a plurality of blocked isocyanate groups in one molecule.
  • a blocked isocyanate group is a group in which an isocyanate group is protected by a reaction with a blocking agent and temporarily inactivated, and when heated to a predetermined temperature, the blocking agent is dissociated to generate an isocyanate group. do.
  • the polyisocyanate compound having a plurality of isocyanate groups for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
  • aromatic polyisocyanate examples include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, and the like.
  • aromatic polyisocyanate examples include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, and the like.
  • examples thereof include m-xylylene diisocyanate and 2,4-tolylen dimer.
  • aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate.
  • a specific example of the alicyclic polyisocyanate is bicycloheptane triisocyanate.
  • the adduct form, the burette form, the isocyanurate form, and the like of the isocyanate compounds mentioned above can be mentioned.
  • isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; Active oxime blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Alcohol-based blocking agents such as ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxi
  • Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol, ethyl thiophenol; acid amide-based blocking agents such as acetate amide and benzamide; imides such as succinate imide and maleate imide.
  • System blocking agents amine blocking agents such as xylidine, aniline, butylamine, dibutylamine; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine; pyrazoles such as dimethylpyrazole Blocking agents and the like can be mentioned.
  • the blocked isocyanate compound may be commercially available, for example, Duranate TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Co., Ltd.), TrixeneBI7982: Blocked isocyanate (hexamethylene isocyanate (HDM) trimer, Blocking agents: dimethylpyrazole (DMP), Baxenden Chemicals) and the like.
  • Duranate TPA-B80E, 17B-60PX, E402-B80T all manufactured by Asahi Kasei Co., Ltd.
  • TrixeneBI7982 Blocked isocyanate (hexamethylene isocyanate (HDM) trimer
  • Blocking agents dimethylpyrazole (DMP), Baxenden Chemicals) and the like.
  • the latent thermosetting component may be a reaction product obtained by reacting an amine compound such as imidazole or dicyandiamide with a hydroxyl group-containing compound, a cyclic ether group-containing compound, a carboxyl group-containing compound, or the like.
  • the content of the thermosetting component (D) is preferably 1 part by mass to 30 parts by mass, and more preferably 5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the curable composition of the present invention. When the content is in this numerical range, the toughness of the cured product and the heat resistance of the solder can be improved.
  • the curable composition of the present invention may contain, if necessary, a colorant, a defoaming / leveling agent, a thixotropy-imparting agent / thickener, a coupling agent, a dispersant, a polymerization inhibitor, a polymerization retarder, a solvent and the like. Can be contained.
  • a solvent may be used for adjusting the viscosity of the curable composition of the present invention, but the amount added is preferably small in order to prevent a decrease in film thickness after curing. Further, it is more preferable that the solvent for adjusting the viscosity is not contained.
  • the curable composition of the present invention has a viscosity suitable for printing by the inkjet method, and therefore can be ejected by an inkjet printer without any trouble. Therefore, the curable composition of the present invention can be used as an ink to directly draw a pattern on a substrate or the like for a printed wiring board.
  • the cured product of the present invention can be obtained by irradiating the curable composition layer immediately after printing with light and photocuring the curable composition layer.
  • Light irradiation is performed by irradiation with active energy rays such as ultraviolet rays, electron beams, and chemical rays, preferably by ultraviolet irradiation.
  • Active energy rays such as ultraviolet rays, electron beams, and chemical rays, preferably by ultraviolet irradiation.
  • Ultraviolet irradiation in an inkjet printer can be performed, for example, by attaching a light source such as a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED to the side surface of the print head, and scanning by moving the print head or the base material. In this case, printing and ultraviolet irradiation can be performed almost at the same time.
  • the curable composition of the present invention contains (D) a thermosetting component
  • a thermosetting component it can be thermoset by using a known heating means, for example, a heating furnace such as a hot air furnace, an electric furnace, or an infrared induction heating furnace. .. In this case, it is preferable to heat at 120 ° C. to 170 ° C. for 5 to 60 minutes.
  • the cured product obtained from the curable composition of the present invention is also excellent in flexibility, it is particularly suitable as a solder resist for a flexible printed wiring board.
  • the substrate of the flexible printed wiring board include a film made of glass polyimide, polyimide, polyethylene terephthalate, liquid crystal polymer, polycarbonate and the like.
  • the present invention also provides a cured product obtained by curing the curable composition of the present invention, and an electronic component having the cured product.
  • the electronic component means a component used in an electronic circuit, and includes a printed wiring board, particularly an active component such as a flexible printed wiring board, a transistor, a light emitting diode, and a laser diode, and other resistors, a capacitor, an inductor, a connector, and the like. Passive components are also included, and the cured product of the curable composition of the present invention is suitable as these insulating cured films.
  • Examples 1 to 5 and Comparative Examples 1 to 3 Each component as shown in Table 1 below was blended in each blending amount, and these were stirred with a dissolver (room temperature, rotation speed 500 rpm, 5 minutes). Then, dispersion was carried out with zirconia beads using a bead mill for 2 hours to obtain a curable composition of the present invention (Examples 1 to 5) and a comparative composition (Comparative Examples 1 to 3).
  • a conical type K-8 (manufactured by Buhra) was used and kneaded under the conditions of a rotation speed of 1200 rpm, a discharge rate of 20%, a bead particle size of 0.65 mm, and a filling rate of 88%.
  • the obtained curable composition was set at 50 ° C., 100 rpm, and 30 seconds, and a cone plate type viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.) was used as a cone rotor at 1 ° 34'x R24.
  • TVE-33H manufactured by Toki Sangyo Co., Ltd.
  • A-TMPT Trimethylol propanetriacrylate; 1,9-nonanediol diacrylate manufactured by Shin-Nakamura Kogyo Co., Ltd .
  • DPGDA Dipropylene glycol diacrylate manufactured by Daiichi Kogyo Seiyaku Co., Ltd .
  • BPE-4 EO-modified bisphenol manufactured by Toyo Chemicals Co., Ltd.
  • FP-100 Phosphazene Compound (Lin Content 13.4%); Fushimi Pharmaceutical Co., Ltd. SPH-100: Phenoxyphosphazene containing phenolic hydroxyl group; Otsuka Co., Ltd. Chemical PX-200: Condensed phosphoric acid ester (phosphorus content 9.0%), Daihachi Chemical Industry Co., Ltd. Pigment Blue 15: 3: Phosphazene blue pigment Pigment Yellow 147: Anthraquinone-based yellow pigment
  • Example of manufacturing evaluation board Each of the curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was applied using an inkjet printing apparatus CPS6151 (manufactured by Microcraft).
  • KM1024iSHE manufactured by Konica Minolta, coating droplet amount 6 pL, number of nozzles 1024, head temperature 50 ° C.
  • Photocuring was performed at 300 mJ / cm 2 using SGHUV-UN-L042-B (manufactured by Microcraft, LED light source, wavelength 365 nm) as a light source.
  • the thermosetting was carried out at 150 ° C. for 60 minutes using a hot air circulation type drying oven DF610 (manufactured by Yamato Scientific Co., Ltd.). The thickness of the cured film was 15 ⁇ m.
  • ⁇ Flame retardant> Kapton in which each of the curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was previously subjected to sulfuric acid treatment using an inkjet printing apparatus CPS6151 (manufactured by Microcraft) as described in the above-mentioned production example of the evaluation substrate. Both sides were coated on 200H to obtain a cured film. Then, the obtained cured film was subjected to a thin lumber vertical combustion test conforming to the UL94 standard. For the evaluation, VTM-0, VTM-1, VTM-2, and Not were judged based on the UL94 standard. The results are summarized in Table 2 below.
  • the evaluation criteria are as follows. Evaluation Criteria ⁇ The average value of the total height of the four ends is 6 mm or less ⁇ The average value of the total height of the four ends exceeds 6 mm and is less than 10 mm ⁇ The average value of the total height of the four ends is 10 mm or more Summarize.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Polymerisation Methods In General (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention vise à fournir : une composition durcissable qui présente des propriétés d'application appropriées pour des procédés d'impression à jet d'encre ; et un produit durci de celui-ci qui présente un faible gauchissement, une résistance à la chaleur de soudure, une résolution et une résistance au feu approprié? en tant que réserve de soudure d'une carte de circuit imprimé flexible. L'invention concerne par conséquent une composition durcissable comprenant les constituants (A) à (D) suivants : (A) trois types de composés ayant un, deux ou trois groupes (méth)acryloyle dans une molécule unique ; (B) un agent ignifuge ayant une structure phosphazène et un groupe phénoxy substitué par un groupe cyano (-CN), un groupe hydroxyle (-OH), ou un groupe méthyle ; (C) un photoinitiateur ; et (D) un composant thermodurcissable, la viscosité de la composition étant inférieure ou égale à 50 mPa·s à 50 °C. L'invention concerne également un produit durci obtenu à partir de ladite composition durcissable. L'invention concerne en outre un composant électronique ayant ledit produit durci.
PCT/JP2021/011345 2020-03-31 2021-03-19 Composition durcissable et produit durci associé Ceased WO2021200267A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116107162A (zh) * 2021-11-09 2023-05-12 上海新阳半导体材料股份有限公司 一种i线光刻胶及其制备方法和应用
CN116107161A (zh) * 2021-11-09 2023-05-12 上海新阳半导体材料股份有限公司 一种i线光刻胶及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008304569A (ja) * 2007-06-05 2008-12-18 Kaneka Corp 感光性樹脂組成物およびその利用
WO2014024951A1 (fr) * 2012-08-08 2014-02-13 旭化成イーマテリアルズ株式会社 Stratifié de film photosensible, carte de circuit imprimé flexible et procédé de fabrication de ceux-ci
JP2015092228A (ja) * 2013-09-30 2015-05-14 株式会社タムラ製作所 感光性樹脂組成物
JP2015173269A (ja) * 2015-04-03 2015-10-01 太陽インキ製造株式会社 プリント配線板用白色硬化型組成物、これを用いた硬化塗膜及びプリント配線板
JP2019061224A (ja) * 2017-09-26 2019-04-18 旭化成株式会社 感光性樹脂フィルム積層体

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5183425B2 (ja) * 2008-11-07 2013-04-17 太陽ホールディングス株式会社 難燃性光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2011116849A (ja) * 2009-12-02 2011-06-16 Kaneka Corp 新規な反応性難燃剤及びその利用
JP2011122086A (ja) * 2009-12-11 2011-06-23 Kaneka Corp 新規な反応性難燃剤及びその利用
JP2016096246A (ja) 2014-11-14 2016-05-26 株式会社東芝 フレキシブルプリント配線板のソルダーレジスト形成方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008304569A (ja) * 2007-06-05 2008-12-18 Kaneka Corp 感光性樹脂組成物およびその利用
WO2014024951A1 (fr) * 2012-08-08 2014-02-13 旭化成イーマテリアルズ株式会社 Stratifié de film photosensible, carte de circuit imprimé flexible et procédé de fabrication de ceux-ci
JP2015092228A (ja) * 2013-09-30 2015-05-14 株式会社タムラ製作所 感光性樹脂組成物
JP2015173269A (ja) * 2015-04-03 2015-10-01 太陽インキ製造株式会社 プリント配線板用白色硬化型組成物、これを用いた硬化塗膜及びプリント配線板
JP2019061224A (ja) * 2017-09-26 2019-04-18 旭化成株式会社 感光性樹脂フィルム積層体

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116107162A (zh) * 2021-11-09 2023-05-12 上海新阳半导体材料股份有限公司 一种i线光刻胶及其制备方法和应用
CN116107161A (zh) * 2021-11-09 2023-05-12 上海新阳半导体材料股份有限公司 一种i线光刻胶及其制备方法和应用
CN116107162B (zh) * 2021-11-09 2025-08-22 上海新阳半导体材料股份有限公司 一种i线光刻胶及其制备方法和应用

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JP2021161191A (ja) 2021-10-11
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CN115315450B (zh) 2024-03-15
CN115315450A (zh) 2022-11-08

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