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
• • 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
  • B41M5/0023—Digital printing methods characterised by the inks used
• • 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
• • 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
  • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/12—Mountings, e.g. non-detachable insulating substrates
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
• • 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 set for inkjet, and more particularly to a curable composition set for two-component inkjet comprising a main agent and a curing agent.
• the present invention also relates to a cured product formed from the two-component inkjet curable composition set, a manufacturing method thereof, a printed wiring board having the cured product, and a fan-out type wafer level package.
• the number of electrodes (terminals and bumps) for external connection of the semiconductor chip tends to increase. Therefore, the pitch of the electrodes for external connection of the semiconductor chip is small. Tend to be. However, it is not always easy to directly mount a semiconductor chip on which bumps are formed at a fine pitch on a circuit board.
• a semiconductor encapsulant region is formed on the outer periphery of the semiconductor chip, and a rewiring layer connected to the electrode is also provided in the semiconductor encapsulant region, so that the bump pitch is reduced. It has been proposed to be larger.
• a WLP is called a fan-out type wafer level package (hereinafter sometimes abbreviated as FO-WLP) because the size of the bump arrangement area is larger than the size of the semiconductor chip.
• a semiconductor chip In FO-WLP, a semiconductor chip is embedded with a semiconductor sealing material. The circuit surface of the semiconductor chip is exposed to the outside, and a boundary between the semiconductor chip and the semiconductor sealing material is formed. A rewiring layer connected to the electrode of the semiconductor chip is also provided in the region of the semiconductor sealing material for embedding the semiconductor chip, and the bump is electrically connected to the electrode of the semiconductor chip through the rewiring layer.
• the pitch of the bumps can be set larger than the pitch of the electrodes of the semiconductor chip.
• a semiconductor chip or an electronic component is arranged at a certain interval on a support, embedded with a semiconductor sealing material, and the sealing material is heat-cured, and then the support.
• Pseudo wafer is produced by peeling from the wafer.
• a rewiring layer is formed from the semiconductor chip circuit surface of the pseudo wafer to the expanded semiconductor sealing material region. In this way, the pitch of the bumps can be set larger than the pitch of the electrodes of the semiconductor chip.
• a positive sensitive resin is applied to the semiconductor chip circuit surface of the pseudo wafer, pre-baked, and activated with UV light or the like in a region to be opened through a photomask or the like. Irradiate light, then develop using a developer such as TMAH (tetramethylammonium hydroxide), heat cure, oxygen plasma treatment, etc., metal electrode sputtering, and further form a photoresist layer
• TMAH tetramethylammonium hydroxide
• heat cure oxygen plasma treatment
• metal electrode sputtering metal electrode sputtering
• the circuit surface (that is, the surface on which the insulating film is formed) is mainly due to shrinkage during curing of the insulating film such as photosensitive polyimide between the wirings. Warping deformation that becomes concave occurs.
• a resin layer is formed on one surface of a substrate made of a wafer-like semiconductor, and the entire resin layer is warped and held in a spherical shape, and then the resin layer is cured.
• Patent Document 2 Has been proposed (for example, Patent Document 2).
• the resin layer for correcting warpage can be formed by applying a resin coating solution over the entire surface of the substrate, but an inkjet method is conceivable as an application method that can be applied separately to a minute region such as a semiconductor chip.
• the ink jet method is a method in which a small amount of liquid droplets are applied to a coating surface from a nozzle and can be applied to a minute and partial application, and is therefore optimal for application to a semiconductor chip or the like.
• the ink jet method in order to facilitate the discharge by the ink jet head, the liquid is discharged from the nozzle after being heated to around 50 ° C.
• blocked isocyanate has been proposed as a thermosetting component (for example, Patent Document 3).
• thermosetting product of isocyanate has a low glass transition temperature, there is a problem that it is not tack-free when heated in a subsequent process, and sticks to a transport device when DRAM is mounted.
• epoxy-based crosslinking is considered optimal from the viewpoint of reaction rate, glass transition temperature, and cost.
• the pot life is short, and clogging of the nozzle and the tank due to gelation is likely to occur when used for a long time at around 50 ° C. .
• the storage stability is shortened.
• a two-pack type curable composition has also been proposed, and a solder resist using a two-pack type epoxy curable composition has also been proposed (for example, Patent Document 4). ). It has also been proposed to apply a two-pack type epoxy curable composition to an ink jet system (for example, Patent Documents 5 and 6). However, since the spread of the liquid at the time of adhesion of the droplet is not considered, it is not suitable for forming a high-definition pattern.
• an object of the present invention is a two-component ink jet that can cope with a high-definition pattern, is tack-free, is suitable for correcting a warp of a pseudo wafer, has excellent heat resistance, and is excellent in dischargeability and storage stability. It is to provide a curable composition set for use. Another object of the present invention is to provide a cured product formed from the two-component inkjet curable composition set, a manufacturing method thereof, a printed wiring board having the cured product, and a fan-out type wafer level package. It is to be.
• the present inventors applied a two-component curable composition having a thermal crosslinking component such as a cyclic ether compound as a main agent and a thermosetting catalyst component as a curing agent to an ink jet system, and separating the main agent and the curing agent separately.
• a thermal crosslinking component such as a cyclic ether compound
• a thermosetting catalyst component as a curing agent
• the active energy ray is irradiated immediately after mixing the main agent and the curing agent, so that the mixing ratio of the main agent and the curing agent can be kept constant, and further, the adhering droplets can be prevented from spreading.
• the curable composition set for inkjet of the present invention is a two-component inkjet curable composition set comprising a main agent and a curing agent,
• the main agent contains a thermal crosslinking component
• the curing agent includes a thermosetting catalyst component;
• Each of the main agent and the curing agent contains a component that cures with active energy rays.
• the thermal crosslinking component may include a cyclic ether compound
• the thermal curing catalyst component may include at least one selected from a basic catalyst and an acidic catalyst.
• the component cured by the active energy ray may be a bifunctional (meth) acrylic monomer.
• both the main agent and the curing agent may contain a photopolymerization initiator.
• both the main agent and the curing agent may contain (meth) acrylic monomers having the same number of functional groups.
• the main agent and the curing agent may each have a viscosity at 50 ° C. in the range of 5 to 100 mPa ⁇ s.
• the main agent and the curing agent are all silica, alumina, titanium oxide, aluminum hydroxide, zinc oxide, zirconium oxide, magnesium oxide, mica, bismuth oxychloride, It may contain at least one inorganic filler selected from the group consisting of talc, kaolin, barium sulfate, silicic anhydride, calcium carbonate, magnesium carbonate, magnesium silicate, aluminum silicate, and aluminum magnesium silicate.
• the curable composition set for inkjet of the present invention may be used as a fan-out type warp correction material for a wafer level package.
• a cured product according to another embodiment of the present invention is a cured product of a mixture of the main agent and the curing agent of the curable composition set for inkjet.
• cured material using the curable composition set for inkjets of another embodiment of this invention discharges the said main agent and the said hardening
• the object to be coated may be a printed wiring board.
• a printed wiring board according to another embodiment of the present invention has the above cured product.
• a fan-out type wafer level package according to another embodiment of the present invention has the cured product.
• high-definition patterns such as high-definition through-holes required for connection to DRAM can be handled, tack-free, suitable for correcting warpage of pseudo wafers, and excellent in heat resistance.
• a cured product formed from the two-component inkjet curable composition set, a manufacturing method thereof, a printed wiring board having the cured product, and a fan-out type wafer level package Can be provided.
• the inkjet curable composition set of the present invention is a two-component inkjet curable composition set comprising a main agent and a curing agent, wherein the main agent includes a thermal crosslinking component, and the curing agent includes a thermosetting catalyst component.
• the main agent and the curing agent are combined into one set.
• the main agent constituting the curable composition set for inkjet includes at least a thermal crosslinking component and a component that is cured by active energy rays.
• curing agent which comprises the curable composition set for inkjets contains at least the thermosetting catalyst component and the component hardened
• “main agent” refers to a composition containing a thermal crosslinking component and no thermosetting catalyst
• curing agent” refers to a composition that promotes crosslinking of the thermal crosslinking component of the main agent.
• the inkjet curable composition set of the present invention includes a component in which both the main agent and the curing agent are cured with active energy rays (hereinafter, sometimes referred to as an active energy ray curable component).
• the active energy ray curable component makes it easy to mix the main agent and the curing agent, and further, when the main agent and the curing agent are mixed, by pre-curing with active energy, the mixed liquid of the main agent and the curing agent is formed. It has the function of keeping the mixing ratio constant by suppressing wetting and spreading.
• the active energy ray-curable component is preferably a curable component that can be subjected to a radical addition polymerization reaction.
• Examples of the curable component capable of undergoing a radical addition polymerization reaction include a radical addition polymerization reactive component having at least one ethylenically unsaturated group in the molecule.
• glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol
• acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, and N, N-dimethylaminopropylacrylamide
• Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate
• polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate
• a polyvalent acrylate such as an ethylene oxide adduct, a propylene oxide adduct, or an ⁇ -caprolactone adduct
• Acrylates, bisphenol A diacrylates, and polyvalent acrylates such as ethylene oxide adduct
• bifunctional (meth) acrylate monomers are particularly preferable from the viewpoint of adjusting the viscosity of the main agent and the curing agent and the compatibility of each component contained in the main agent and the curing agent.
• the active energy ray-curable components contained in the main agent and the curing agent are preferably (meth) acrylate monomers having the same number of functional groups.
• the following compounds (1) to (11) may be used as curable components that can be cured by radical addition polymerization reaction contained in the main agent and the curing agent.
• a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide is reacted with an unsaturated group-containing monocarboxylic acid, and the resulting reaction product is converted to a polybasic acid.
• (Meth) acrylated acrylic-containing urethane resin (8) During the synthesis of a resin by polyaddition reaction of a diisocyanate with a carboxyl group-containing dialcohol compound and a diol compound, a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule is added, Terminal (meth) acrylated acrylic-containing urethane resin, (9) An acrylic-containing urethane resin obtained by adding a compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule during the synthesis of the resin of (5), and terminal (meth) acrylated, (10) An acrylic-containing urethane resin obtained by adding a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule during the synthesis of the resin of (5) above, and terminally (meth) acrylated; 11) An acrylic-containing polymer obtained by adding a compound having one epoxy group
• the active energy ray-curable component is preferably contained in an amount of 10% to 90% by mass in the main agent and 10% to 90% by mass in the curing agent. If it is in the range of 10% by mass to 90% by mass, curing with active energy rays may be good.
• the main agent and the curing agent constituting the inkjet composition set of the present invention preferably further contain a photopolymerization initiator for causing the above-described active energy curable component to undergo a polymerization reaction with active energy rays.
• a photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6- Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxy) Benzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,
• oxime esters hereinafter referred to as “oxime ester photopolymerization initiators”
• ⁇ -aminoacetophenone light which is one of acetophenones.
• photopolymerization initiators selected from the group consisting of “polymerization initiators” and acylphosphine oxides (hereinafter referred to as “acylphosphine oxide photopolymerization initiators”).
• oxime ester photopolymerization initiator examples include commercially available products such as CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by BASF Japan, and N-1919 manufactured by ADEKA.
• numerator can also be used suitably.
• ⁇ -aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like.
• Commercial products include Omnirad 907, Omnirad 369, Omnirad 379 manufactured by IGM Resins.
• acylphosphine oxide photopolymerization initiator examples include the above compounds.
• Commercially available products include Omnirad TPO, Omnirad 819 manufactured by IGM Resins.
• an oxime ester photopolymerization initiator as a photopolymerization initiator that causes radical addition polymerization reaction with active energy rays, not only can a sufficient amount be obtained, but also when a thermosetting component is blended. Since there is little volatilization of the photopolymerization initiator in the post-heating process during thermosetting and mounting, contamination of a device such as a drying furnace can be reduced.
• acylphosphine oxide photopolymerization initiator when used, the deep curability at the time of photoreaction is improved, so that a favorable opening (through hole) shape can be obtained in terms of resolution.
• photopolymerization initiators that cause radical addition polymerization reaction with active energy rays may be used.
• Yueyang Kimoutain Sci-tech Co. , Ltd., Ltd. JMT-784 made by the company can be preferably used.
• the main component of the curable composition set for inkjet of the present invention contains a thermal crosslinking component.
• the thermal crosslinking component include thermosetting components having at least one selected from the group consisting of two or more cyclic ether groups and cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups). It is done.
• the cyclic ether compound is particularly preferable in that a tack-free coating film is obtained by advancing the thermal crosslinking reaction and increasing the glass transition temperature (hereinafter sometimes abbreviated as Tg).
• thermosetting component having two or more cyclic (thio) ether groups in the molecule is either one of the three-, four- or five-membered cyclic ether groups in the molecule, or the cyclic thioether group, or two of them.
• a compound having at least two epoxy groups in the molecule that is, a polyfunctional epoxy compound, a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional compound.
• examples include oxetane compounds, compounds having two or more thioether groups in the molecule, that is, episulfide resins.
• a polyfunctional epoxy compound is preferable in that crosslinking easily proceeds.
• polyfunctional epoxy compound examples include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840 manufactured by DIC Corporation, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD- manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. 011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Ltd. E. R. 330, A.I.
• Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, manufactured by DIC Corporation, Epototo YDCN-701, YDCN-704, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., EPPN-201, EOCN, manufactured by Nippon Kayaku Co., Ltd. -1025, EOCN-1020, EOCN-104S, RE-306, Sumi-epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd. E. R.
• ECN-235, ECN-299, etc. both trade names
• novolac epoxy resins DIC Corporation Epicron 830, Mitsubishi Chemical Corporation jER807, Nippon Steel & Sumikin Chemical Co., Ltd.
• Epototo YDF-170, YDF-175 Bisphenol F type epoxy resins such as YDF-2004 (all trade names); hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
• Glycidylamine type epoxy resin such as jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YH-434 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all trade names); hydantoin type Epoxy resin; Cellokisai manufactured by Daicel Corporation Mitsubishi Chemical Co., Ltd. of YL-933, manufactured by Dow Chemical Co., T.; 2021P, etc. alicyclic epoxy resin (trade name) E. N. , EPPN-501, EPPN-502, etc.
• Bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Tetraphenylolethane type epoxy resin such as jERYL-931 (all trade name) manufactured by Mitsubishi Chemical Corporation; Nissan Chemical Industries Heterocyclic Epoxy (trade name) manufactured by TEPIC, Inc.
• Diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; tetraglycidyl xylenoylethane resin such as ZX-1063 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
• Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, and EXA-4700 manufactured by DIC Corporation; Epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; CP-50S, CP-50M and other glycidyl methacrylate copolymer epoxy resins; cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Corporation) ), Although CTBN modified epoxy resin (for example, manufactured by Nippon Steel Sumitomo Metals Chemical Co.
• CTBN modified epoxy resin for example, manufactured by Nippon Steel Sumitomo Metals Chemical Co.
• YR-102, YR-450, etc. and the like, not limited thereto.
• These epoxy resins can be used alone or in combination of two or more.
• a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.
• Polyfunctional oxetane compounds include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolac resin, poly (P-hydroxystyrene), card
• Examples of the episulfide resin that is a compound having two or more cyclic (thio) ether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
• thermosetting components may include known and commonly used thermosetting resins such as isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, polyimide compounds, and episulfide resins. .
• the thermal crosslinking component is preferably contained in the main agent in an amount of 1 to 70% by mass.
• the thermal crosslinking component is contained in the range of 1% by mass to 50% by mass, the viscosity may be low and the ejection property may be good.
• the curing agent constituting the curable composition set for inkjet of the present invention contains a thermosetting catalyst component.
• a thermosetting catalyst component a compound that advances the curing reaction when mixed with the above-described main agent and heated can be used.
• Examples of the basic catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, melamine, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N- And amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine, phosphine compounds such as tributylphosphine and triphenylphosphine, and hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide.
• imidazole 2-methyl
• Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds), DBU, DBN, U-CATSA102, manufactured by Shikoku Kasei Kogyo Co., Ltd. U-CAT5002 (both bicyclic amidine compounds and salts thereof). These basic catalysts may be used individually by 1 type, or may be used in combination of 2 or more types as appropriate.
• Examples of the acid catalyst for the thermosetting catalyst include novolak resin type and acid anhydride type.
• Examples of the novolak resin type include phenol novolak resin, cresol novolak resin, bisphenol novolak resin, poly p-vinylphenol, and the like. These novolak resin-based acidic catalysts may be used alone or in combination of two or more.
• Examples of the acid anhydride acid catalyst include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-chlorophthalic anhydride, and 4-chlorophthalic anhydride.
• Acid benzophenone tetracarboxylic anhydride, succinic anhydride, methyl succinic anhydride, dimethyl succinic anhydride, dichlor succinic anhydride, methyl nadic acid, dodecyl succinic acid, chlorendec anhydride, maleic anhydride, 3,6-endomethylenetetrahydro anhydride Phthalic acid, hexachloroendomethylenetetrahydrophthalic anhydride, methyl-3,6-endomethylenetetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1 , 2-Dicarboxylic anhydride, ethyl Glycol bisanhydrotrimellitate, glycerin bis (anhydrotrimellitate) monoacetate, and the like.
• These acid anhydride acid catalysts may be used alone or in combination of two or more.
• the inkjet curable composition set of the present invention is composed of a main component containing a thermal crosslinking component and a curing agent containing a thermosetting catalyst as separate compositions, so that it is preserved compared to a one-component curable type. Excellent stability.
• the main component and the curing agent constituting the curable composition set for inkjet of the present invention preferably contain an inorganic filler component from the viewpoint of controlling the physical properties of the coating film.
• an inorganic filler component conventionally known ones can be used without limitation, for example, silica, alumina, titanium oxide, aluminum hydroxide, zinc oxide, zirconium oxide, magnesium oxide, mica, bismuth oxychloride, as the inorganic filler, Talc, kaolin, barium sulfate, silicic anhydride, calcium carbonate, magnesium carbonate, magnesium silicate, aluminum silicate, magnesium aluminum silicate, silicon carbide, silicon nitride, boron nitride, glass powder, metal oxide, metal powder, etc. 1 type can be used individually or in mixture of 2 or more types.
• the inorganic filler component does not necessarily need to be included in both the main agent and the curing agent, and may be included in either one.
• the inorganic filler component preferably has an average particle size of 0.01 to 5 ⁇ m, more preferably 0.02 to 2 ⁇ m.
• the average particle diameter is the number average particle diameter calculated as an arithmetic average value obtained by measuring the major axis diameter of 20 inorganic fillers randomly selected with an electron microscope.
• the main agent and the curing agent constituting the curable composition set for inkjet of the present invention preferably include a colorant component.
• Including a colorant component prevents the semiconductor device from malfunctioning due to infrared rays or the like generated from surrounding devices when a semiconductor chip on which a cured product formed from the ink-jet curable composition set is placed in a device. can do.
• a cured product is engraved by means such as laser marking, marks such as characters and symbols can be easily recognized.
• the product number is usually printed on the surface of the protective film by a laser marking method (a method in which the surface of the protective film is scraped off and printed by laser light).
• a laser marking method a method in which the surface of the protective film is scraped off and printed by laser light.
• the main agent and the curing agent contain a colorant, a sufficient difference in contrast between the portion of the protective film scraped by the laser beam and the portion not removed is obtained, and the visibility is improved.
• the colorant component is not necessarily included in both the main agent and the curing agent, and may be included in either one.
• organic or inorganic pigments and dyes can be used singly or in combination of two or more.
• black pigments are preferable from the viewpoint of electromagnetic wave and infrared shielding properties.
• the black pigment include carbon black, perylene black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like, but are not limited thereto.
• Carbon black is particularly preferable from the viewpoint of preventing malfunction of the semiconductor device.
• pigments or dyes such as red, blue, green, and yellow can be mixed to obtain black or a black color close thereto.
• red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Specific examples include the following: It is done.
• blue colorants include phthalocyanine series and anthraquinone series, and pigment series are compounds classified as Pigment, specifically: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4. Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60, and the like.
• the dye system include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 70, Solvent Blue 70, and Solvent Blue 70
• metal-substituted or unsubstituted phthalocyanine compounds can also be used.
• the green colorant there are similarly phthalocyanine, anthraquinone, perylene, and the like. Specifically, PigmentGreen 7, PigmentGreen 36, SolventGreen 3, SolventGreen 5, SolventGreen 20, SolventGreen 28, and the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
• the green colorant there are similarly phthalocyanine, anthraquinone, perylene, and the like. Specifically, PigmentGreen 7, PigmentGreen 36, SolventGreen 3, SolventGreen 5, SolventGreen 20, SolventGreen 28, and the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
• yellow colorants examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
• colorants such as purple, orange, brown and black may be added for the purpose of adjusting the color tone.
• the coupling agent component having a functional group that reacts with an inorganic substance and a functional group that reacts with an organic functional group may be included in the main agent and the curing agent that constitute the curable composition set for inkjet of the present invention. At least one of the adhesion of the warp correction layer to the adherend (pseudo wafer), adhesion and cohesiveness of the warp correction layer when the warp correction layer is provided on FO-WLP using the curable composition set for inkjet One can be improved.
• a coupling agent component when a coating film of a mixture composed of a main agent and a curing agent is formed on FO-WLP and the mixture is cured to form a warp correction layer, the heat resistance of the warp correction layer is reduced.
• Examples of such coupling agents include titanate coupling agents, aluminate coupling agents, silane coupling agents, and the like. Of these, silane coupling agents are preferred.
• the coupling agent is not necessarily included in both the main agent and the curing agent, and may be included in either one.
• Examples of organic groups contained in the silane coupling agent include vinyl groups, epoxy groups, styryl groups, methacryloxy groups, acryloxy groups, amino groups, ureido groups, chloropropyl groups, mercapto groups, polysulfide groups, and isocyanate groups. Can be mentioned.
• Commercially available silane coupling agents can be used, for example, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403.
• KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM -573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all trade names; manufactured by Shin-Etsu Silicon Chemical Co., Ltd.) Can be mentioned. These may be used alone or in combination of two or more.
• additives may be blended in the main agent and the curing agent constituting the curable composition set for inkjet of the present invention, if necessary.
• Various additives include leveling agents, plasticizers, antioxidants, ion scavengers, gettering agents, chain transfer agents, release agents, rust inhibitors, adhesion promoters, UV absorbers, thermal polymerization inhibitors, thickening agents.
• You may contain a well-known and usual additive in the field
• the main agent and the curing agent constituting the curable composition set for inkjet according to the present invention may contain an organic solvent.
• the organic solvent is used to adjust the viscosity when synthesizing a polyether compound containing an ethylenically unsaturated group in the molecule, mixing each component, and applying the obtained curable resin composition to a substrate or a support film. Can be used for.
• organic solvent examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether a
• the main component and the curing agent containing each of the above components can be applied to a high-definition desired pattern by using an inkjet method, and a cured product can be obtained by curing the coating film.
• the main agent and the curing agent preferably have a viscosity at 50 ° C. of 5 to 100 mPa ⁇ s, particularly 5 to 50 mPa ⁇ s. Thereby, smooth printing can be performed without applying an unnecessary load to the ink jet printer.
• the viscosity of the main agent and the curing agent can be adjusted mainly by the content of the active energy ray-curable component such as the above-described bifunctional (meth) acrylic monomer.
• the method for adhering the main agent and the curing agent to the object to be coated by the ink jet method is not particularly limited.
• the main agent starts from a separate nozzle of the ink jet printer. It is preferable to discharge the curing agent and the curing agent so as to adhere to substantially the same position on the object to be coated.
• the main agent and the curing agent adhere to substantially the same position on the object to be coated, so that both are mixed.
• substantially the same position refers to a state in which when the droplets ejected from separate inkjet nozzles adhere to the object to be coated, both droplets overlap and the main agent and the curing agent can be mixed. It is not intended to cause the droplets to adhere to exactly the same location.
• the active energy ray is irradiated after the main agent and the curing agent are adhered to the same position on the object to be coated.
• the active energy ray curable component contained in the main agent and the curing agent is cured by irradiation with the active energy ray, and the coating film in which the main agent and the curing agent are mixed is cured or the viscosity of the coating film is increased. It is possible to prevent the attached coating film from spreading. Therefore, it is preferable that the irradiation with the active energy ray is performed as soon as possible after the main agent and the curing agent are attached to the object to be coated.
• the active energy rays are preferably irradiated within 1.0 second, more preferably within 0.5 second.
• High-definition patterning can be performed by irradiating active energy rays promptly after ejection.
• the direction of irradiating the active energy ray to the coating film to which the main agent and the curing agent are attached is not particularly limited, but from the oblique side of the coated object or when the coated object is transparent, Active energy rays can be irradiated from the back surface direction.
• LED low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, etc. are suitable as the active energy ray irradiation light source.
• electron beams, ⁇ rays, ⁇ rays, ⁇ rays, X rays, neutron rays, and the like can also be used.
• the number of irradiation light sources is one, or two or more. In the case of two or more, light sources having different wavelengths can be used in combination.
• the irradiation amount of the active energy ray varies depending on the film thickness of the coating film, but is generally in the range of 10 to 10,000 mJ / cm 2 , preferably 20 to 2000 mJ / cm 2 , more preferably 100 to 2000 mJ / cm 2. be able to.
• a warp correction layer provided on the surface can be formed.
• a printed wiring board can be formed as a solder resist by an ink jet method as described above.
• the coating film irradiated with the active energy ray is finally cured by heat to become a cured product.
• the conditions (temperature, time, etc.) for thermosetting vary depending on the use of the cured product formed using the two-component inkjet curable composition set.
• a fan-out type wafer level package will be described as an example.
• a semiconductor wafer is prepared and a circuit is formed on one surface.
• the semiconductor wafer may be a silicon wafer or a compound semiconductor wafer such as gallium arsenide (GaAs).
• GaAs gallium arsenide
• a circuit can be formed on the wafer surface by various methods including a widely used method such as an etching method and a lift-off method.
• the semiconductor wafer may be cut into individual semiconductor chips through a dicing process.
• the semiconductor chip obtained as described above is placed on a plate-like carrier having a smooth surface through an adhesive layer.
• a carrier A circular or square silicon wafer and a metal plate can be used.
• the adhesive layer a layer capable of temporarily fixing a semiconductor chip and capable of being peeled off after manufacturing a pseudo wafer is used.
• an acrylic adhesive, a rubber adhesive, a styrene / conjugated diene block copolymer, or the like can be used as such an adhesive layer material.
• a carboxyl group-containing resin having an ethylenically unsaturated group and a radical polymerization initiator as described above can be contained.
• heating or active energy rays can be contained.
• the adhesiveness of the adhesive layer can also be changed by irradiation.
• the semiconductor chips to be mounted may be the same or different in the number of arrangement in the vertical and horizontal directions in plan view, and from various viewpoints such as improving the density and securing the terminal area per unit semiconductor chip, You may arrange
• the distance between the adjacent semiconductor chips is not particularly limited, but may be arranged so as to obtain a fan-out (FO) region necessary for forming a connection terminal of the finally obtained FO-WLP. desirable.
• the semiconductor chip placed on the plate-like carrier via the adhesive layer is sealed with a sealing material.
• the semiconductor chip is placed and the sealing material is applied or bonded onto the carrier so that the side wall surface and the upper surface of the semiconductor chip are sealed with the sealing material.
• the sealing material is molded so as to be embedded in the space between the semiconductor chips.
• the sealing step using such a sealing material can be formed by performing compression molding using a known semiconductor sealing resin composition that is liquid, granule, or sheet.
• Known resin encapsulating resin compositions mainly include epoxy resins, epoxy resin curing catalysts, curing accelerators, spherical fillers, and the like.
• the plate-like carrier After curing the sealing material, the plate-like carrier is peeled off. Peeling is performed between the sealing material and the semiconductor chip and the adhesive layer.
• peeling method heat treatment is performed to change (decrease) the adhesive strength of the adhesive layer and release, or first peeling is performed between the plate-like carrier and the adhesive layer, and then the adhesive layer is subjected to heat treatment or Examples of the method include a method of releasing after the irradiation treatment with an electron beam or ultraviolet rays.
• the post-cure may be carried out on the pseudo wafer thus obtained. Post-curing is performed, for example, at a temperature range of 150 to 200 ° C. and a range of 10 minutes to 8 hours. Subsequently, the pseudo wafer can be thinned by polishing the opposite side of the obtained pseudo wafer where the semiconductor is embedded.
• the grinding method is not particularly limited, and grinding may be performed by a known means using a grinder or the like.
• the thickness of the pseudo wafer after grinding is not particularly limited, but is usually about 50 to 500 ⁇ m.
• a rewiring layer is formed on the side of the pseudo wafer where the semiconductor chip circuit is exposed.
• a rewiring insulating resin is applied to the entire surface of the pseudo wafer where the semiconductor chip circuit is exposed by spin coating or the like, and prebaked at about 100 ° C. to form a rewiring insulating resin layer. To do.
• a pattern is formed on the insulating resin layer for rewiring using a photolithography method or the like, and heat treatment (curing) is performed.
• the heat treatment conditions are, for example, a temperature range of 150 to 250 ° C. and a range of 10 minutes to 5 hours.
• insulating resin for rewiring Although it does not specifically limit as insulating resin for rewiring, From a heat resistant and reliable viewpoint, a polyimide resin, a polybenzooxide resin, a benzocyclobutene resin etc. are used. As described above, when the insulating resin for rewiring is heat-treated, the pseudo wafer may be warped due to heat shrinkage of the insulating resin.
• a power feeding layer is formed on the entire surface of the rewiring layer surface of the pseudo wafer by a method such as sputtering, then a resist layer is formed on the power feeding layer, exposed to a predetermined pattern and developed, and then via and copper are plated by electrolytic copper plating.
• a rewiring circuit is formed. After forming the rewiring circuit, the resist layer is peeled off and the power feeding layer is etched.
• solder resist layer may be formed so as to cover a part of the rewiring circuit and the solder balls.
• the applied flux can be resin-based or water-based. As the heating and melting method, reflow, hot plate or the like can be used. In this way, a pseudo wafer of FO-WLP is obtained.
• the FO-WLP is obtained by dividing the FO-WLP pseudo wafer into individual pieces by a method such as dicing.
• a warp correction layer is formed on the surface opposite to the surface on which the rewiring layer of the pseudo wafer thus obtained is formed.
• the warp correction layer is formed by an inkjet method using a two-component inkjet curable composition set. That is, the main agent and the curing agent are ejected from an ink jet nozzle and adhered to substantially the same position to form a coating film, and the coating film is cured by irradiation with active energy rays. After that, by heating as described later, the coating film is further cured to form a warp correction layer.
• the warp correction layer may be formed on the entire surface opposite to the surface on which the rewiring layer of the pseudo wafer is formed, or the warp correction layer may be formed so as to achieve a desired patterning.
• the ink jet method fine and partial printing is possible, and the location and size of the warp of the package can be flexibly dealt with.
• the coating amount of the warp correction material is preferably adjusted so that the thickness of the warp correction layer when cured to form the warp correction layer is in the range of 15 to 50 ⁇ m. If the thickness of the warp correction layer is 15 ⁇ m or more, it becomes easy to smooth the warp. If it is 50 ⁇ m or less, the thinness, which is one of the advantages of FO-WLP, is not impaired.
• the application amount of the warp correction material that is, the adjustment of the thickness of the warp correction layer after curing the warp correction material, the irradiation amount of the active energy ray, and further, the selection of the whole surface irradiation and partial irradiation
• the amount of correction according to the degree of warpage of FO-WLP can be easily adjusted by appropriately adjusting the degree of cure of the warp correction layer of the pseudo wafer.
• the temperature and time for curing by heat are adjusted, or the temperature of the pseudo wafer is warped by performing a method of raising the temperature in one step to the target temperature or performing step heating that is heated to the final temperature via an intermediate temperature.
• the amount of correction can be easily adjusted by appropriately adjusting the degree of cure of the correction layer and the warping of FO-WLP.
• the temperature for curing by heating is 100 ° C. to 300 ° C., more preferably 120 ° C. to 180 ° C.
• the time for curing by heating is preferably 30 seconds to 3 hours. Preferably, it is 30 minutes to 2 hours.
• the curing temperature is 120 ° C. to 180 ° C.
• the time for curing by heating is preferably 30 minutes to 2 hours.
• ⁇ Preparation of pseudo wafer> A 4-inch, 150 ⁇ m thick P-type silicon wafer having a 100 nm SiO 2 film formed on one side made by Canosis Co., Ltd. was diced using a dicing apparatus to obtain a 10 mm ⁇ 10 mm square semiconductor chip.
• a temporary fixing film was placed on a SUS flat substrate, and the above-mentioned semiconductor chips were placed 5 ⁇ 5 in length and breadth so that the SiO 2 surface was in contact with the temporarily fixing film and the distance between the semiconductor chips was 10 mm vertically and horizontally.
• a 100 mm ⁇ 100 mm square sheet-shaped semiconductor encapsulant was laminated thereon so that the center positions were approximately the same, and compression-molded at 150 ° C.
• a kneaded material having the following composition is placed between two 50 ⁇ m cover films (Teijin Purex film), and the kneaded material is formed into a sheet by a flat plate pressing method. What was formed in the sheet form of 200 micrometers in thickness was used.
• ⁇ Preparation of semiconductor encapsulant composition The following components were blended, heated at 70 ° C. for 4 minutes in a roll kneader, then heated at 120 ° C. for 6 minutes, and melt-kneaded for 10 minutes in total with reduced pressure (0.01 kg / cm 2) to prepare a kneaded product.
• ⁇ Naphthalene type epoxy resin Nippon Kayaku Co., Ltd.
• NC-7000 30 parts by mass / bisphenol type epoxy resin (YX-4000 manufactured by Mitsubishi Chemical Corporation) 10 parts by mass / phenol novolac type epoxy resin (DEN 431 manufactured by The Dow Chemical Company) 10 parts by mass, 2 parts by mass of anthraquinone, carbon black (carbon MA-100, manufactured by Mitsubishi Chemical Corporation) 10 parts by mass, spherical silica (Admafine Inc. Admafine SO-E2) 500 parts by mass, silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass, 2-phenylimidazole (2PZ, manufactured by Shikoku Chemicals Co., Ltd.) 2 parts by mass
• the temporarily fixed film was peeled off from the obtained laminate, and the back side was polished to obtain a pseudo wafer having a size of 100 mm ⁇ 100 mm square and a thickness of 200 ⁇ m.
• a positive type rewiring forming resin composition having the following composition was applied by spin coating to the semiconductor circuit surface side of the obtained pseudo wafer, and prebaked by heating at 100 ° C. for 20 minutes.
• the thickness of the photosensitive rewiring-forming resin layer formed on the pre-baked pseudo wafer was 10 ⁇ m.
• HMW680GW metal halide lamp
• ORC organic halide lamp
• a photomask in which a circular opening pattern of 100 ⁇ m is continuously formed vertically and horizontally at a pitch of 400 ⁇ m
• an exposure amount of 500 mJ / cm 2 is positive.
• the mold pattern was irradiated with light, and developed using a 2.38 wt% TMAH aqueous solution at 25 ° C. for 2 minutes to form a rewiring resin layer in which a round opening pattern was formed.
• the amount of warpage was a state in which the central portion was recessed by 6 mm with reference to a peripheral portion of 100 mm ⁇ 100 mm square.
• ⁇ Preparation of warp correction layer> A piezo ink jet printer was used, and an ink cartridge having a discharge amount of 10 pl (per discharge) was used.
• the main agent and the curing agent having the following composition were filled in separate cartridges, and the ejection amounts of the main agent and the curing agent were the same and the landing positions were the same.
• the exposure was performed within 0.5 seconds after landing with a high-pressure mercury lamp attached to the side.
• the exposure amount was 600 mJ / cm 2 , and the coated film after irradiation was heated at 160 ° C. for 60 minutes in a BOX-type drying furnace to produce a warp correction layer.
• Omnirad 369 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (manufactured by IGM Resins) 8 parts by mass, MA-100: carbon black (manufactured by Mitsubishi Chemical Corporation) 1 part by mass, BYK-307: silicon-based additive (by Big Chemie Japan) 0.1 parts by mass
• Main agent 3 and curing agent 3 were prepared in the same manner except that HDDA and DPGDA contained in each of main agent 1 and curing agent 1 were replaced with 50 parts by mass of ⁇ -butyllactone (manufactured by Mitsubishi Chemical Corporation).
• curable composition 4 for inkjet ⁇ Preparation of curable composition 4 for inkjet> The following components were blended, mixed and dispersed by a bead mill, and filtered through a glass fiber filter having a pore size of 1 ⁇ m to obtain a curable composition 4 for inkjet.
• Block isocyanate (manufactured by Baxenden) 20 parts by mass, 4HBA: 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.) 3 parts by mass ⁇ HDDA: 1,6-hexanediol diacrylate (manufactured by Daicel Ornex) 10 parts by mass ⁇ DPGDA: dipropylene glycol diacrylate (manufactured by BASF Japan Ltd.) 50 parts by mass ⁇ Omnirad 369: 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) -butanone (IGM Resins) 8 parts by mass ⁇ MA-100: carbon black (manufactured by Mitsubishi Chemical Corporation) 1 part by mass ⁇ BYK-307: silicon-based additive (by Big Chemie Japan) 0.1 parts by mass
• the ejection characteristics of the set of the main agent 2 and the curing agent 3 and the set of the main agent 3 and the curing agent 3 were similarly evaluated. Further, the ink jet curable compositions 4 and 5 were filled in one of the ink cartridges, and the same dischargeability evaluation was performed. The evaluation criteria were as follows. ⁇ : No nozzle clogged ⁇ : Nozzle clogged
• Viscosity change rate (%)
• the storage stability was evaluated based on the following criteria. ⁇ : Viscosity change rate within 10%
• the curable composition set for an ink jet comprising a main agent and a curing agent, the main agent including a thermal crosslinking component, the curing agent including a thermosetting catalyst component,
• the curable composition set for inkjets containing a component that is cured with active energy rays (Examples 1 and 2), ejection properties, and correction of the warpage of the pseudo wafer (from the result of the warpage of the pseudo wafer), Heat resistance, tack-free property (from the result of confirmation of tack property), and storage stability were all good.
• active energy rays Examples 1 and 2
• a one-pack type curable composition for inkjet (Comparative Examples 1 and 2) and a two-part type curable composition for inkjet composed of a main agent and a curing agent, the main component including a thermal crosslinking component.
• the curing agent contains a thermosetting catalyst component but neither the main agent nor the curing agent contains a component that cures with active energy rays. It has been difficult to simultaneously correct the warpage of the pseudo wafer, heat resistance, tack-free property, and storage stability.

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