Curable resin composition, method for protecting the edge of a substrate, and method for manufacturing a substrate.

Abstract

The present invention provides a curable resin composition that protects the edge surface of a substrate and prevents the generation of foreign matter from the edge surface. [Solution] A carboxyl group-containing photopolymerizable monomer having a weight-average molecular weight of 100 to 300 and a viscosity of 100 to 10,000 mPa·s at 25°C, A polyfunctional photopolymerizable monomer having a viscosity of 10 mPa·s or less at 25°C, Inorganic fillers, Photopolymerization initiator and A curable resin composition containing [a specific ingredient].

Description

Technical Field

[0001] The present invention relates to a curable resin composition, a method for protecting an end face of a substrate, and a method for manufacturing a substrate.

Background Art

[0002] From the viewpoint of improving the yield in the manufacture of substrates such as printed wiring boards, in recent years, management of the surface state of substrates has been attracting attention. In the manufacturing process of substrates, when a cutting process is performed on a substrate, fine dust (foreign matter) is generated at the cutting portion. Such foreign matter causes problems such as poor contact of the substrate circuit and deterioration of quality. Therefore, it is preferable to remove such foreign matter. As a method for removing foreign matter on a substrate, for example, the methods described in Patent Documents 1, 2, etc. are known.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, with the methods described in Patent Documents 1 and 2, only dust removal on the substrate surface can be performed, and dust removal on the substrate end face cannot be performed. Therefore, dust adhering to the substrate end face may adhere to the substrate surface during work. In addition, since the end face of the substrate is fragile, there is also a risk of collapse and generation of further foreign matter. Therefore, there has been a demand for a technique for forming a protective film on the end face of the substrate to prevent the generation of foreign matter.

[0005] An object of the present invention is to provide a curable resin composition capable of protecting the end face of a substrate and preventing the generation of foreign matter from the end face. Another object of the present invention is to provide a method for protecting the end face of a substrate and a method for manufacturing a substrate. [Means for solving the problem]

[0006] To solve the above problems, the inventors conducted extensive research and found that it is possible to protect the edges of a substrate by using a curable resin composition containing a carboxyl group-containing photopolymerizable monomer having a weight-average molecular weight of 100 to 300 and a viscosity of 100 to 10,000 mPa·s at 25°C, a polyfunctional photopolymerizable monomer having a viscosity of 10 mPa·s or less at 25°C, an inorganic filler, and a photopolymerization initiator.

[0007] This invention was completed based on these findings and includes the following broad embodiments of the invention. [Section 1] A carboxyl group-containing photopolymerizable monomer having a weight-average molecular weight of 100 to 300 and a viscosity of 100 to 10,000 mPa·s at 25°C, A polyfunctional photopolymerizable monomer having a viscosity of 10 mPa·s or less at 25°C, Inorganic fillers, Photopolymerization initiator and A curable resin composition containing [a specific ingredient]. [Section 2] The curable resin composition according to claim 1, wherein the carboxyl group-containing photopolymerizable monomer comprises at least one selected from the group consisting of 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, and 2-(meth)acryloyloxyethyl succinic acid. [Section 3] The curable resin composition according to claim 1 or 2, wherein the polyfunctional photopolymerizable monomer comprises at least one selected from the group consisting of 2-(allyloxymethyl)acrylic acid ester, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate. [Section 4] The curable resin composition according to any one of claims 1 to 3, wherein the inorganic filler comprises at least one selected from the group consisting of silica, talc, and barium sulfate. [Section 5] A curable resin composition according to any one of items 1 to 4, wherein the viscosity at 25°C is 300 dPa·s or less. [Section 6] A curable resin composition according to any one of items 1 to 5, for dispenser application. [Section 7] (1) A step of applying a curable resin composition described in any one of items 1 to 6 to the edge surface of a substrate, (2) A step of forming a cured product by irradiating the curable resin composition with ultraviolet light, A method for protecting the edge of a substrate, including the method described above. [Section 8] (3) Step of peeling off the cured product under alkaline conditions The method described in paragraph 7, further including the method described in paragraph 7. [Section 9] (i) A step of applying a curable resin composition according to any one of items 1 to 6 to the edge surface of a substrate, (ii) A step of forming a cured product by irradiating the curable resin composition with ultraviolet light, (iii) A step of forming a resist pattern on a substrate, (iv) A step of etching the substrate obtained in step (iii), (v) Steps to remove the cured product and resist under alkaline conditions, A method for manufacturing a substrate, including the following. [Effects of the Invention]

[0008] According to the present invention, a curable resin composition capable of protecting the edge surface of a substrate and preventing the generation of foreign matter from the edge surface can be provided. Furthermore, a method for protecting the edge surface of a substrate using the curable resin composition and a method for manufacturing a substrate can also be provided. [Brief explanation of the drawing]

[0009] [Figure 1] A schematic diagram showing the application of the curable resin composition of the present invention to the edge surface of a substrate using a dispenser, from a direction approximately perpendicular to the substrate edge. [Modes for carrying out the invention]

[0010] In this specification, "(meth)acrylate" means at least one selected from the group consisting of acrylate (acrylic acid ester) and methacrylate (methacrylic acid ester). Further, when expressing a numerical range as "A~B" using "~", unless otherwise specified, this means "A or more and B or less".

[0011] 1. Curable resin composition The curable resin composition of the present invention contains a carboxyl group-containing photopolymerizable monomer having a weight average molecular weight of 100 to 300 and a viscosity at 25°C of 100 to 10,000 mPa·s, a polyfunctional photopolymerizable monomer having a viscosity at 25°C of 10 mPa·s or less, an inorganic filler, and a photopolymerization initiator.

[0012] <Carboxyl group-containing photopolymerizable monomer> The curable resin composition of the present invention contains a carboxyl group-containing photopolymerizable monomer having a weight average molecular weight of 100 to 300 and a viscosity at 25°C of 100 to 10,000 mPa·s. The carboxyl group-containing photopolymerizable monomer having a weight average molecular weight of 100 to 300 and a viscosity at 25°C of 100 to 10,000 mPa·s is a photopolymerizable monomer having one or more carboxyl groups and one or more photopolymerizable groups in one molecule, having a weight average molecular weight in the range of 100 to 300, and having a viscosity at 25°C of 100 to 10,000 mPa·s.

[0013] Examples of the photopolymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an allyloxy group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, an oxetanyl group, etc. Among them, an acryloyloxy group, a methacryloyloxy group, and an allyloxy group are preferable, and an acryloyloxy group is more preferable.

[0014] The weight-average molecular weight of the carboxyl group-containing photopolymerizable monomer is 100 to 300, preferably 150 to 280. If the weight-average molecular weight is less than 100, the strength of the cured coating film decreases, which is undesirable. Also, if the weight-average molecular weight is greater than 300, the viscosity of the curable resin composition increases, and the applicability decreases, which is also undesirable.

[0015] The viscosity of the carboxyl group-containing photopolymerizable monomer at 25°C is 100 to 10,000 mPa·s, with 1,000 to 10,000 mPa·s being more preferable, 3,000 to 9,000 mPa·s even more preferable, and 6,000 to 8,000 mPa·s particularly preferable, in order to obtain better touch-drying properties and etching resistance. The "viscosity" is measured in accordance with JIS Z 8803:2011, item 10, "Method for measuring viscosity using a cone-plate rotational viscometer," at 25°C, 50 rpm, and 30 seconds, using a 3° × R14 cone rotor and a cone-plate viscometer (Toki Sangyo Co., Ltd., TVE-33H).

[0016] The carboxyl group-containing photopolymerizable monomer is preferably a compound obtained by reacting a photopolymerizable monomer having one or more alcoholic hydroxyl groups in one molecule with a polybasic acid anhydride.

[0017] Examples of photopolymerizable monomers having one or more alcoholic hydroxyl groups in one molecule include (meth)acrylate compounds such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate. These compounds may be used individually or in combination of two or more.

[0018] Examples of polybasic acid anhydrides to be added to the above-mentioned photopolymerizable monomer having an alcoholic hydroxyl group include succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, dodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, and the like. These compounds may be used individually or in combination of two or more.

[0019] Examples of carboxyl group-containing photopolymerizable monomers include 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxypropyl succinic acid, and 2-(meth)acryloyloxypropyl maleic acid, among which 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, and 2-(meth)acryloyloxyethyl succinic acid are preferred. These compounds may be used individually or in combination of two or more.

[0020] Examples of commercially available carboxyl group-containing photopolymerizable monomers include light acrylate HOA-MPL(N), HOA-HH(N), and HOA-MS(N) manufactured by Kyoeisha Chemical Co., Ltd., and NK ester A-SA, NK ester SA, and NK ester CB-1 manufactured by Shin Nakamura Chemical Co., Ltd.

[0021] The content of the carboxyl group-containing photopolymerizable monomer in the curable resin composition of the present invention is preferably 20 to 80% by mass, more preferably 30 to 75% by mass, and particularly preferably 40 to 70% by mass, based on the total amount of the curable resin composition.

[0022] <Multifunctional photopolymerizable monomers> The curable resin composition of the present invention contains a polyfunctional photopolymerizable monomer having a viscosity of 10 mPa·s or less at 25°C. A polyfunctional photopolymerizable monomer having a viscosity of 10 mPa·s or less at 25°C is a photopolymerizable monomer having two or more photopolymerizable groups in one molecule and having a viscosity of 10 mPa·s or less at 25°C.

[0023] Examples of photopolymerizable groups include vinyl groups, vinyloxy groups, 1-chlorovinyl groups, isopropenyl groups, 4-vinylphenyl groups, allyloxy groups, acryloyloxy groups, methacryloyloxy groups, oxyranyl groups, and oxetanyl groups. Among these, acryloyloxy groups, methacryloyloxy groups, and allyloxy groups are preferred.

[0024] The viscosity of the polyfunctional photopolymerizable monomer at 25°C is 10 mPa·s or less, preferably between 1 and 9 mPa·s. If the viscosity at 25°C exceeds 10 mPa·s, it is undesirable because it reduces the coatability of the curable resin composition and the alkali peelability of the cured coating film of the curable resin composition. The viscosity can be measured in accordance with JIS Z 8803:2011, section 10, "Method for measuring viscosity using a cone-plate rotational viscometer," at 25°C, 50 rpm, and 30 seconds, using a 3° × R14 cone rotor and a cone-plate viscometer (Toki Sangyo Co., Ltd., TVE-33H).

[0025] Examples of the polyfunctional photopolymerizable monomers include 2-(allyloxymethyl)acrylic acid esters such as methyl 2-(allyloxymethyl)acrylate, ethyl 2-(allyloxymethyl)acrylate, propyl 2-(allyloxymethyl)acrylate, and butyl 2-(allyloxymethyl)acrylate, as well as 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate. Among these, 2-(allyloxymethyl)acrylic acid ester, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate are preferred. These compounds may be used individually or in combination of two or more.

[0026] Examples of commercially available polyfunctional photopolymerizable monomers include AOMA from Nippon Shokubai Co., Ltd., Viscoat #230,HDDA, Viscoat #195,1,4-BDDA, and Viscoat #260,1,9-NDDA from Osaka Organic Industries Co., Ltd., and NK ester A-HD-N, NK ester A-NOD-N, NK ester A-DOD-N, NK ester A-NPG, NK ester HD-N, NK ester NOD-N, NK ester DOD-N, and NK ester NPG from Shin Nakamura Chemical Industry Co., Ltd.

[0027] The content of the polyfunctional photopolymerizable monomer in the curable resin composition of the present invention is preferably 10 to 60 parts by mass, and more preferably 15 to 55 parts by mass, per 100 parts by mass of the carboxyl group-containing photopolymerizable monomer.

[0028] <Inorganic filler> The inorganic filler used in the curable resin composition of the present invention can be any known or commonly used one without particular limitation. By adding an inorganic filler, adhesion to the substrate can be improved.

[0029] Examples of inorganic fillers include silica such as talc, amorphous silica, crystalline silica, fused silica, and spherical silica; kaolin, montmorilloid, montmorillonite, clay, Neuburg silica particles, boehmite, synthetic mica, hydrotalcite, zeolite, silicon nitride, aluminum nitride, calcium zirconate, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, barium titanate, calcium carbonate, calcium silicate, lithium carbonate, gold, aluminum, copper, nickel, carbon black, carbon nanotubes, and graphite. Among these, silica, talc, and barium sulfate are preferred. These may be used individually or in combination of two or more.

[0030] The shape of the inorganic filler is not particularly limited and can be spherical, fibrous, plate-shaped, amorphous, balloon-shaped, etc. The average particle size of the inorganic filler is also not particularly limited and can be, for example, 0.01 to 3.0 μm. Furthermore, the inorganic filler may be subjected to various surface treatments, such as insulation treatment or high-dispersibility treatment, as needed.

[0031] The inorganic filler content in the curable resin composition of the present invention is preferably 30 to 200 parts by mass, more preferably 35 to 100 parts by mass, and particularly preferably 40 to 80 parts by mass, per 100 parts by mass of the carboxyl group-containing photopolymerizable monomer.

[0032] <Photopolymerization initiator> As the photopolymerization initiator used in the curable resin composition of the present invention, any known or conventionally used agent can be used without particular limitation.

[0033] Examples of photopolymerization initiators include α-aminoacetophenone-based photopolymerization initiators such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 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, 1-hydroxycyclohexylphenyl ketone, 1-[4-( Hydroxyacetophenone-based photopolymerization initiators such as 2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenyl phosphine Sphin oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethyl Acyl phosphine oxide-based photopolymerization initiators such as benzoyl)-phenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinate methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinate isopropyl ester, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide;Benzoin-based photopolymerization initiators such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ether-based photopolymerization initiators; benzophenone-based photopolymerization initiators such as benzophenone, p-methylbenzophenone, Michlar's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone Acetophenone-based photopolymerization initiators such as 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone; thioxanthone-based photopolymerization initiators such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone Anthraquinone-based photopolymerization initiators such as chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketal-based photopolymerization initiators such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid ester-based photopolymerization initiators such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoate ethyl ester; 2-(O-benzoyloxime)- Oxime ester-based photopolymerization initiators such as 1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyloxime); titanocene-based photopolymerization initiators such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyr-1-yl)ethyl)phenyl]titanium;Examples include the following. Among these, anthraquinone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and oxime ester-based initiators are preferred. These may be used individually or in combination of two or more.

[0034] Commercially available α-aminoacetophenone-based photopolymerization initiators include Omnirad 907, 369, 369E, and 379 from IGM Resins. Commercially available acylphosphine oxide-based photopolymerization initiators include TPO from Kusumoto Chemicals, Inc. and Omnirad 819 from IGM Resins. Commercially available anthraquinone-based photopolymerization initiators include 2-ethyl AQ from Mitsui & Co. Chemicals Ltd. Commercially available oxime ester-based photopolymerization initiators include Irgacure OXE01 and OXE02 from BASF Japan Ltd., N-1919 from ADEKA Corporation, ADEKA Arclus NCI-831 and NCI-831E, and TR-PBG-304 from Changzhou Strong Electronic New Materials Co., Ltd.

[0035] Furthermore, the content of the photopolymerization initiator in the curable resin composition of the present invention is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 7 parts by mass, per 100 parts by mass of the carboxyl group-containing photopolymerizable monomer.

[0036] <Other ingredients> The curable resin composition of the present invention may optionally contain further components (additives) such as polymerization inhibitors, surfactants, co-sensitizers, ultraviolet absorbers, antioxidants, ion catchers, coupling agents, tackifiers, surface modifiers, leveling agents, defoamers, rheology control agents, and pigments, to the extent that the effects of the present invention are exhibited.

[0037] The content of other components in the curable resin composition of the present invention is preferably 0.01 to 10% by mass relative to the total amount of the curable resin composition.

[0038] The content of organic solvent in the curable resin composition of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less, based on the total amount of the curable resin composition. A content of 1% by mass or less allows for the omission of the solvent drying step, simplifying the process. It is also preferable because it prevents sagging during the drying process. In one embodiment, the curable resin composition of the present invention contains no organic solvent (0% by mass).

[0039] <Preparation of curable resin composition> The curable resin composition of the present invention is prepared as a homogeneous liquid composition by mixing the above-mentioned carboxyl group-containing photopolymerizable monomer, the above-mentioned polyfunctional photopolymerizable monomer, an inorganic filler, and a photopolymerization initiator, along with other components as needed.

[0040] The viscosity of the curable resin composition of the present invention at 25°C is preferably 300 dPa·s or less, more preferably 250 dPa·s or less, and particularly preferably 220 dPa·s or less, from the viewpoint of coatability. Furthermore, the lower limit of viscosity is preferably 10 dPa·s or more from the viewpoint of coatability. The "viscosity" can be measured in accordance with JIS Z 8803:2011, item 10, "Method for measuring viscosity using a cone-plate type rotational viscometer," at 25°C, 50 rpm, and 30 seconds, using a 3°×R14 cone rotor and a cone-plate type viscometer (Toki Sangyo Co., Ltd., TVE-33H).

[0041] 2. Uses of curable resin compositions In one embodiment, the curable resin composition of the present invention can be applied to the edge surface of a substrate and cured with ultraviolet light to form a protective film on the substrate edge surface. With the protective film formed on the edge surface, etching or other treatments can be performed on the substrate surface to suppress defects caused by foreign matter originating from the substrate edge surface. Furthermore, after the substrate surface treatment, the protective film on the substrate edge surface can be removed to obtain the substrate. Details are described below.

[0042] <Method for protecting the edges of a substrate> In one embodiment, a method for protecting the edge of a substrate using the curable resin composition of the present invention is provided. The method includes the following steps. (1) A step of applying the curable resin composition of the present invention to the edge surface of a substrate. (2) A step of forming a cured product by irradiating the curable resin composition with ultraviolet light.

[0043] In step (1), the curable resin composition of the present invention is applied to the edge surface of the substrate. The application of the curable resin composition of the present invention to the edge surface of the substrate is preferably performed from a direction substantially perpendicular to the edge surface. More preferably, the substrate is placed horizontally, and the curable resin composition of the present invention is applied to the edge surface from a substantially horizontal direction. In this specification, "substantially perpendicular direction" means approximately ±20° with respect to the vertical direction, with a preferred degree of approximately ±10°. Also, in this specification, "substantially horizontal direction" means approximately ±20° with respect to the horizontal direction, with a preferred degree of approximately ±10°. Figure 1 shows a schematic diagram of applying the curable resin composition of the present invention to the edge surface of the substrate from a direction substantially perpendicular to the edge surface using a dispenser. When the substrate in Figure 1 is placed horizontally, the curable resin composition of the present invention is applied to the edge surface from a substantially horizontal direction.

[0044] Examples of substrates include printed circuit boards and flexible printed circuit boards with circuits pre-formed using copper, as well as copper-clad laminates using paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluororesin / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate, etc., and other materials such as metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, and wafers.

[0045] In step (1) described above, it is preferable to use a dispenser to apply the curable resin composition of the present invention to the substrate edge. Examples of dispensers include jet dispensers, air dispensers, monopump dispensers, screw dispensers, and handgun dispensers. Among these, it is more preferable to use a jet dispenser because it is possible to eject droplets with high precision from a position far from the point of impact (the point where the droplets land).

[0046] The inner diameter of the dispensing port provided in the dispenser can be appropriately determined according to the viscosity of the curable resin composition and the amount of liquid dispensed at one time, but for example, it is preferably 0.05 to 1 mm in diameter, and more preferably 0.1 to 0.5 mm in diameter.

[0047] The amount of liquid droplets of the curable resin composition dispensed at one time is preferably 100 μL to 1 μL, and more preferably 50 μL to 5 μL.

[0048] The dispensing frequency is not particularly limited, but is preferably 1 ms / shot to 10 s / shot, and more preferably 1 ms / shot to 10 ms / shot. The nozzle movement speed is also not particularly limited, but is preferably 1 to 300 mm / sec, and more preferably 50 to 100 mm / sec. However, these dispensing frequencies and nozzle movement speeds can be set as appropriate.

[0049] Examples of dispensers used in the above process (1) include, but are not limited to, AeroJet, CyberJet, CyberJet 2 manufactured by Musashi Engineering Co., Ltd., NEO-JET manufactured by Iwashita Engineering Co., Ltd., high-precision jet dispensers manufactured by San-ei Tech Co., Ltd., DispenseJet series (PICOPμlse) manufactured by Nordson Corporation, and piezo jet dispensers (StreamJet Valve) manufactured by SSI Japan Co., Ltd.

[0050] In step (2), a cured product is formed by irradiating the curable resin composition applied to the substrate edge surface in step (1) with ultraviolet light.

[0051] The peak wavelength of the ultraviolet light used for irradiation is typically 200-450 nm, preferably 250-420 nm, and more preferably 300-405 nm.

[0052] Examples of light sources for ultraviolet irradiation include UV-LEDs (light-emitting diodes), UV-LDs (laser diodes), mercury lamps, metal halide lamps, and ultraviolet fluorescent lamps. Of these, UV-LEDs and UV-LDs are preferred from the viewpoint of being small, having a long lifespan, and being highly efficient.

[0053] The cumulative amount of ultraviolet light (UV exposure) is typically 300-5000 mJ / cm². 2 The concentration is preferably 500-2000 mJ / cm². 2 That is the case.

[0054] The thickness of the cured product of the curable resin composition obtained by the above step (2) is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, and even more preferably 10 μm to 30 μm. This thickness can be measured using a micrometer.

[0055] The substrate obtained by step (2) above, which has a cured material on its edge face, can be subjected to surface treatment (for example, formation of a resist film on the substrate surface, etching of the substrate, etc.). Since the cured material made from the curable resin composition of the present invention has excellent adhesion to the substrate and etching resistance, various treatments can be performed on the substrate with the cured material on its edge face. Furthermore, by performing various treatments with the cured material on the edge face of the substrate, the generation of foreign matter originating from the edge face of the substrate can be suppressed, and defects caused by foreign matter originating from the edge face of the substrate can be reduced.

[0056] In one embodiment, the method for protecting the end face of the substrate is: (3) A step of peeling off the cured product under alkaline conditions, It may further contain the following. In a preferred embodiment, the cured product made from the curable resin composition of the present invention is used for the purpose of temporarily protecting the substrate edge. Therefore, it is preferable to peel the cured product off the substrate edge after performing various treatments on the substrate surface.

[0057] For alkaline conditions, for example, an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide can be used. By immersing a substrate with a cured material on its end face in these alkaline aqueous solutions, the cured material can be easily removed. The concentration of the alkaline substance, such as sodium hydroxide or potassium hydroxide, is preferably 1 to 5% by mass. The temperature of the alkaline aqueous solution is preferably 30 to 60°C. The immersion time is preferably within 7 minutes, more preferably within 5 minutes, and particularly preferably within 3 minutes.

[0058] <Manufacturing method for substrates> In one embodiment, a method for manufacturing a substrate using the curable resin composition of the present invention is provided. The method includes the following steps. (i) A step of applying the curable resin composition of the present invention to the edge surface of the substrate. (ii) A step of forming a cured product by irradiating the curable resin composition with ultraviolet light. (iii) A step of forming a resist pattern on a substrate. (iv) A step of etching the substrate obtained in step (iii). (v) A step of removing the cured product and resist under alkaline conditions.

[0059] In step (i), the curable resin composition of the present invention is applied to the edge surface of the substrate. This step is the same as step (1) in the above-described <Method for protecting the edge surface of the substrate>, and the embodiments described above can be applied without particular limitation.

[0060] In step (ii), a cured product is formed by irradiating the curable resin composition applied to the substrate edge surface in step (i) with ultraviolet light. This step is the same as step (2) in the <Method for protecting the substrate edge surface> described above, and the embodiments described above can be applied without particular limitation.

[0061] In step (iii), a resist pattern is formed on the substrate obtained in step (ii) above, which has a cured material on its edge face. The resist pattern can be formed, for example, by forming a resist film on the substrate, followed by exposure and development processes.

[0062] The resist film can be formed using any known method without particular limitations. For example, methods include laminating a resist film onto a substrate, or applying a solution of a resist composition onto a substrate and curing the resist composition by heating or the like to form a coating film. In the method of applying a solution of a resist composition onto a substrate and curing the resist composition by heating or the like to form a coating film, the application method to the substrate can be spin coating, slit coating, roll coating, curtain coating, screen printing, or applicator coating.

[0063] If necessary, a pretreatment may be performed on the substrate with a cured material on its edge face before the formation of the resist film. The pretreatment can be carried out using any known method without particular limitations. Examples include acid treatment, physical polishing such as buffing, and chemical polishing.

[0064] The formed resist film is hardened by exposure (light irradiation). Specifically, the exposed area can be hardened by exposure with radiation through a photomask having a desired pattern, or by directly exposing the pattern using a direct exposure machine. Here, radiation refers to ultraviolet rays, visible light, far ultraviolet rays, X-rays, electron beams, etc., and the light source can be a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc., but for example, when using a high-pressure mercury lamp, it is 100 to 1500 mJ / cm². 2 That is the case.

[0065] For development after irradiation, an alkaline aqueous solution (for example, a 0.3-3% by mass sodium carbonate aqueous solution) is used as the developer to dissolve and remove unwanted unexposed areas, leaving only the exposed areas, thereby obtaining a cured film with the desired pattern.

[0066] Since the cured product made from the curable resin composition of the present invention is resistant to resist pattern formation operations such as resist film formation, exposure, and development, the operations can be performed while maintaining the cured product on the substrate edge. Because the above operations can be performed while protecting the substrate edge, there is no concern that the substrate edge will collapse during the operation and generate foreign matter.

[0067] In step (iv), the substrate with the resist pattern formed in step (iii) is etched. The etching process etches away the parts of the substrate that are not covered by the resist (parts other than the resist pattern). This makes it possible to obtain a substrate etched with the desired pattern.

[0068] Etching methods include dry etching using oxygen plasma and wet etching using an etching solution, which can be appropriately selected depending on the material of the substrate, the precision of the pattern, and the application of the substrate. Preferred wet etching solutions include ferric chloride and cupric chloride, and the etching solution temperature is preferably 30°C to 50°C.

[0069] Since the cured body made from the curable resin composition of the present invention is resistant to the above etching process, etching can be performed while maintaining the cured material on the substrate edge. Because etching can be performed while protecting the substrate edge, there is no concern that the substrate edge will collapse and generate foreign matter during the etching process.

[0070] In step (v), the cured product and resist made from the curable resin composition of the present invention are peeled off under alkaline conditions.

[0071] For alkaline conditions, for example, an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide can be used. By immersing a substrate with a cured material on its end face in these alkaline aqueous solutions, the cured material can be easily removed. The concentration of the alkaline substance, such as sodium hydroxide or potassium hydroxide, is preferably 1 to 5% by mass. The temperature of the alkaline aqueous solution is preferably 30 to 60°C. The immersion time is preferably within 7 minutes, more preferably within 5 minutes, and particularly preferably within 3 minutes.

[0072] In one embodiment, it is preferable to remove both the cured product made from the curable resin composition of the present invention and the resist pattern (the resist film in the portion that was photocured during exposure) together under alkaline conditions. Therefore, it is preferable that the photocured resist film can be peeled off from the substrate under the same conditions as the cured product made from the curable resin composition of the present invention.

[0073] Thus, in the manufacturing of substrates, by protecting the substrate edge with a cured body made from the curable resin composition of the present invention, the generation of foreign matter originating from the substrate edge during substrate manufacturing can be suppressed, and defects caused by foreign matter originating from the substrate edge can be reduced. [Examples]

[0074] The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

[0075] <Materials used> HOA-MPL(N): Manufactured by Kyoeisha Chemical Co., Ltd., a mixture of carboxyl group-containing acrylate, 2-acryloyloxyethyl phthalic acid, etc., Mw: 269, 7000 mPa·s @ 25℃ HOA-HH(N): Manufactured by Kyoeisha Chemical Co., Ltd., carboxyl group-containing acrylate, 2-acryloyloxyethylhexahydrophthalic acid, Mw: 270, 4500 mPa·s @ 25℃ HOA-MS(N): Manufactured by Kyoeisha Chemical Co., Ltd., carboxyl group-containing acrylate, 2-acryloyloxyethyl succinic acid, Mw: 216, 180 mPa·s @ 25℃ • Evecryl 270: Manufactured by Daicel Ornex Co., Ltd., bifunctional urethane acrylate, Mw: 1500, 3000 mPa·s @ 60℃ • AOMA: Manufactured by Nippon Shokubai Co., Ltd., 2-(allyloxymethyl)methyl acrylate, bifunctional photopolymerizable monomer, 2 mPa·s @ 25℃ • HDDA: Manufactured by Osaka Organic Industries Co., Ltd., 1,6-hexanediol diacrylate, bifunctional photopolymerizable monomer, 7 mPa·s @ 25℃ • NK Ester A-NOD-N: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., 1,9-nonanediol diacrylate, bifunctional photopolymerizable monomer, 8 mPa·s @ 25℃ • NK Ester A-NPG: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., neopentyl glycol diacrylate, bifunctional photopolymerizable monomer, 6 mPa·s @ 25℃ • Aronix M-120: Manufactured by Toagosei Co., Ltd., EO2 molar added 2-ethylhexyl acrylate, monofunctional photopolymerizable monomer, 7 mPa·s @ 25℃ • Arronix M-221B: Manufactured by Toagosei Co., Ltd., EO2 molar added bisphenol A diacrylate, bifunctional photopolymerizable monomer, 1100 mPa·s @ 25℃ • TMPTA: Manufactured by Daicel Ornex Corporation, trimethylolpropane triacrylate, trifunctional photopolymerizable monomer, 80 mPa·s @ 25℃ • 2-Ethyl AQ: Manufactured by Mitsui & Co. Chemicals, Ltd., 2-ethylanthraquinone, photopolymerization initiator TPO: 2,4,6-trimethylbenzoyldipenylphosphine oxide, manufactured by Kusumoto Chemical Co., Ltd., photopolymerization initiator. • Spectra K: Manufactured by Paudex Corporation, silane coupling treated talc • Barium sulfate 110: Manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate • Crystallite 5X: Manufactured by Ryumori Co., Ltd., silica • Typeque CR-97-Super-70: Manufactured by Ishihara Sangyo Co., Ltd., rutile-type titanium oxide. • Phthalocyanine blue: Manufactured by DIC Corporation, blue pigment

[0076] <Examples 1-10, Comparative Examples 1-4> The curable resin compositions of Examples 1-10 and Comparative Examples 1-4 were prepared by mixing each component in the proportions and compositions shown in Tables 1 and 2 below, then finely dispersing the initiator and other components using a three-roll mill, filtering the resulting composition through a 10 μm aperture filter, and finally degassing it using a centrifugal degasser at 1800 rpm for 2 minutes. Unless otherwise specified, the numerical values ​​in Tables 1 and 2 refer to "parts by mass". Each prepared curable resin composition was evaluated as described below. The results are shown in Tables 1 and 2. Note that sagging properties were not evaluated for the curable resin compositions of Comparative Examples 1 to 4.

[0077] <Viscosity> In accordance with JIS Z 8803:2011, section 10, "Method for measuring viscosity using a cone-plate rotational viscometer," the values ​​were measured at 25°C, 50 rpm, and 30 seconds. A 3°×R14 cone rotor was used, and measurements were taken using a cone-plate viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.).

[0078] <Applicability> A buffed and flattened copper-clad substrate was coated with a jet dispenser having a 0.3 mm diameter nozzle, with a distance of 1 mm from the nozzle tip to the substrate. The composition was then applied to form a 20 mm × 20 mm × 20 μm square after curing, and the dispensing state was visually observed. LED (365 nm) 1,000 mJ / cm² was also used. 2 The material was cured by irradiation, and the shape of the cured material was observed visually. Based on the results of the visual observation, the applicability of the composition was evaluated according to the following criteria. ◎: The composition is continuously dispensed from the nozzle, and the width of the dispensed composition is uniform. ○: The composition is continuously dispensed from the nozzle. △: The composition is dispensed discontinuously from the nozzle. ×: The composition is not dispensed from the nozzle.

[0079] <Method for preparing substrates for evaluating cured coatings> On a buffed and flattened copper-clad substrate, a jet dispenser with a 0.3mm diameter nozzle was used to coat the composition, ensuring a distance of 1mm from the nozzle tip to the substrate. After curing, the mixture formed a 20mm x 20mm x 20μm square. Subsequently, a 1,000mJ / cm² LED (365nm) was applied. 2 The substrate was irradiated and used for evaluating the cured coating.

[0080] <Dryness to the touch> The touch-dry properties of the cured coatings prepared using the above-described substrate preparation method were evaluated according to the following criteria. ◎: The cured coating is completely non-sticky. ○: The hardened coating has a slight stickiness. △: The cured coating is noticeably sticky. ×: The hardened coating has a strong sticky texture.

[0081] <Adhesion to glass> A 1mm thick soda-lime glass was wiped with a cloth soaked in isopropanol, and the isopropanol was allowed to dry. Next, using a jet dispenser with a nozzle diameter of 0.3mmΦ, the composition was applied to the substrate at a distance of 1mm from the nozzle tip, forming a 20mm × 20mm × 20μm square after curing. Subsequently, it was subjected to an LED (365nm) at a concentration of 1,000mJ / cm². 2 The coating was cured by irradiation. 100 grids were formed on the cured coating using a 1 mm wide cross-cut guide, and the number of remaining grids was evaluated by peeling cellophane tape over them according to the following criteria. ○: The number of remaining squares is 90 or more. △: The number of remaining squares is 60 or more but less than 90. ×: The number of remaining squares is less than 60.

[0082] <Etching resistance> The cured coating film prepared using the above-described method for preparing a substrate for evaluating the cured coating film was immersed in a ferric chloride solution at 40°C for 5 minutes, and the state of the cured coating film was then visually evaluated. ◎: The cured coating film is not affected at all by the ferric chloride solution. ○: The cured coating film is hardly eroded by the ferric chloride solution. △: The hardened coating film is slightly eroded by the ferric chloride solution. ×: The hardened coating film has been completely eroded by the ferric chloride solution.

[0083] <Alkaline peeling properties> The cured coating film prepared using the above-described method for preparing a substrate for evaluating the cured coating film was immersed in a 3% by mass NaOH aqueous solution at 50°C, and the time it took for the cured coating film to completely peel off from the copper was measured and evaluated according to the following criteria. ◎: The time it takes for the hardened coating to completely peel off the copper is less than 3 minutes. ○: The time it takes for the hardened coating to completely peel off the copper is between 3 and 5 minutes. △: The time it takes for the hardened coating to completely peel off the copper is between 5 and 7 minutes. ×: The time it took for the hardened coating to completely peel off the copper was more than 7 minutes.

[0084] [Table 1]

[0085] [Table 2]

[0086] The curable resin compositions of Examples 1 to 10 showed good results in terms of applicability, touch-drying properties, adhesion, etching resistance, and alkali peelability. On the other hand, the curable resin compositions of Comparative Examples 1 to 4 were outside the scope of the present invention, and therefore showed inferior results compared to the present invention in at least one of the following areas: poor applicability, low adhesion, poor etching resistance, or poor alkali peelability. [Explanation of Symbols]

[0087] 11 circuit boards 12 Edge of the substrate 21 Dispensers 31 Droplets of curable resin composition

Claims

1. A carboxyl group-containing photopolymerizable monomer having a weight-average molecular weight of 100 to 300 and a viscosity of 100 to 10,000 mPa·s at 25°C, A polyfunctional photopolymerizable monomer having a viscosity of 10 mPa·s or less at 25°C, Inorganic fillers, Photopolymerization initiator and A curable resin composition containing [a specific ingredient].

2. The curable resin composition according to claim 1, wherein the carboxyl group-containing photopolymerizable monomer comprises at least one selected from the group consisting of 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, and 2-(meth)acryloyloxyethyl succinic acid.

3. The curable resin composition according to claim 1, wherein the polyfunctional photopolymerizable monomer comprises at least one selected from the group consisting of 2-(allyloxymethyl) acrylic acid ester, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate.

4. The curable resin composition according to claim 1, wherein the inorganic filler comprises at least one selected from the group consisting of silica, talc, and barium sulfate.

5. The curable resin composition according to claim 1, wherein the viscosity at 25°C is 300 dPa·s or less.

6. A curable resin composition according to claim 1, for use with a dispenser.

7. (1) A step of applying the curable resin composition described in claim 1 to the end face of a substrate, and (2) A step of forming a cured product by irradiating the curable resin composition with ultraviolet light, A method for protecting the edge of a substrate, including the method described above.

8. (3) Step of peeling off the cured product under alkaline conditions The method according to claim 7, further comprising:

9. (i) A step of applying the curable resin composition according to claim 1 to the end face of a substrate, (ii) A step of forming a cured product by irradiating the curable resin composition with ultraviolet light, (iii) A step of forming a resist pattern on a substrate, (iv) A step of etching the substrate obtained in step (iii), (v) Steps to remove the cured product and resist under alkaline conditions, A method for manufacturing a substrate, including the following.

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