Resist composition and laminate thereof

Abstract

The present invention relates to a resist composition and its laminate, belonging to the technical field of preparing printed circuit components. The resist composition comprises the following raw materials in parts by mass: 50-65 parts of an alkali-soluble resin, 30-45 parts of a photopolymerizable monomer, 0.5-5.0 parts of a photoinitiator, and nano-silica, with the added amount being 0-0.1 parts by mass, based on 100 parts by mass of the total of the alkali-soluble resin and the photopolymerizable monomer. Compared to existing technologies, the resist composition described herein produces lower developer foam height during development; laminates formed therefrom exhibit less tendency to gel flow and better storage stability.

Description

Technical Field

[0001] The invention relates to an anti-etching agent composition and a laminate thereof, belonging to the technical field of preparation of circuit printing elements. Background Art

[0002] Dry film resist is widely used as a key material for pattern transfer in printed circuit boards (PCBs), lead frames, solar cells, conductor packages, BGAs (Ball Grid Arrays), and CPSs (Chip Size Packages). For example, in PCB manufacturing, dry film resist is first applied to a copper substrate. A mask with a specific pattern is then placed over the resist to expose the pattern. A weakly alkaline aqueous solution is then used as a developer to remove the unexposed areas. Etching or electroplating is then performed to form the pattern. Finally, a strong alkaline aqueous solution is used as a stripper to remove the cured dry film, achieving pattern transfer.

[0003] Typically, resists are fabricated into a resist laminate (i.e., a photosensitive dry film) structured as a support film layer, a resist layer, and a protective film layer. The support and protective film layers primarily support and protect the resist layer located in the middle layer. However, during storage, the resist layer can easily flow between the support and protective film layers, or even squeeze out of them. This can lead to uneven thickness and undesirable issues such as disconnection during pattern transfer. To improve this storage stability, significant efforts have been made. For example, Chinese invention patent application number CN 201610034685.0 discloses a storage-stable photosensitive dry film and its preparation method. This method uses a preheated slitting blade to cure the edges of the dry film laminate during slitting, leaving a 1-2 mm thick solidified layer along the edges to prevent the resist from flowing out of the edges. This method has significant technical benefits, but it also complicates the production process and reduces production efficiency.

[0004] In addition, during the production of printed circuit boards, a large amount of foam is easily generated during the development process. The developer is continuously carried away by the foam, causing the liquid level to drop significantly, resulting in insufficient development pressure, affecting the side morphology of the dry film after development, and seriously affecting the normal production. Therefore, the industry hopes to have a dry film resist with low development foam. Summary of the Invention

[0005] In order to solve the above problems, the present invention provides a resist composition, which has better storage stability and lower development foam height without deteriorating other properties of the resist.

[0006] The technical solutions of the present invention for solving the above problems are as follows:

[0007] The resist composition comprises an alkali-soluble resin, a photopolymerizable monomer and a photoinitiator, and further comprises nano-silicon dioxide. As a preferred embodiment of the above technical solution, the nano-silicon dioxide has a specific surface area of ​​100 m 2 / g; the nano-silica is added in an amount of less than 0.1 parts by mass, based on the total mass of the alkali-soluble resin and the photopolymerizable monomer as 100 parts by mass.

[0008] In the above technical solution of the present invention, the nano-silica is preferably hydrophobic nano-silica, which can be pre-dispersed in a diluent by grinding, ultrasound, or the like. Examples include Evonik Degussa's AEROSIL series products, including R202 (specific surface area 100), R972 (specific surface area 110), R8200 (specific surface area 160), R974 (specific surface area 170), R816 (specific surface area 190), and R812 (specific surface area 260).

[0009] The original particle size of nano-silica is generally 7-40nm, but after being dispersed into the solution, it is prone to aggregation. The particle size after dispersion is larger than the original particle size. From the perspective of defoaming effect, resolvability, and adhesion, the smaller the particle size, the better.

[0010] As a preferred solution, the nano-silica dispersion is filtered before use or after being added to the resist composition solution and fully dispersed to form a resist composition coating liquid. The filtration accuracy is below 5 microns. The purpose of the filtration is to remove a small amount of large-sized agglomerated particles and other impurities.

[0011] As a preferred embodiment of the above technical solution, the resist composition further comprises a surfactant, and the surfactant is added in an amount of 0 to 3.0 parts by mass based on 100 parts by mass of the total mass of the alkali-soluble resin and the photopolymerizable monomer.

[0012] As a further preferred embodiment of the above technical solution, the surfactant is added in an amount of 0.5 to 2.9 parts by mass based on 100 parts by mass of the total alkali-soluble resin and the photopolymerizable monomer.

[0013] As a preferred embodiment of the above technical solution, the surfactant is a non-ionic surfactant.

[0014] As a preferred embodiment of the above technical solution, the nonionic surfactant is selected from one or more of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene alkyl ester, polyoxyethylene ether, polyoxypropylene ether, polyoxyethylene-polyoxypropylene block copolymer, nonylphenol polyoxyethylene ether, polyoxyethylene alkyl acyl alcohol amine, polyoxyethylene alkylamine, glyceryl monostearate, pentaerythritol ester, and sorbitan ester.

[0015] As a preferred embodiment of the above technical solution, the resist composition further includes additives, such as dyes such as diamond green and Victoria blue B, photocolorizers such as colorless crystal violet, color-forming heat stabilizers, plasticizers, pigments, fillers, flame retardants, stabilizers, leveling agents, stripping accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc.

[0016] As a preferred embodiment of the above technical solution, the alkali-soluble resin is a carboxyl-containing vinyl resin obtained by copolymerization of at least one unsaturated carboxylic acid and at least one vinyl compound.

[0017] The unsaturated carboxylic acid includes, but is not limited to, (meth)acrylic acid, crotonic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and crotonic acid.

[0018] The vinyl compound includes, but is not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, styrene, α-methylstyrene, hydroxystyrene, (meth)acrylamide, N-hydroxymethyl-acrylamide, N-butoxymethyl-acrylamide, phenoxyethyl (meth)acrylate, (alkoxylated) nonylphenol (meth)acrylate, N,N-dimethylethyl (meth)acrylate, N,N-diethylethyl (meth)acrylate, N,N-dimethylpropyl (meth)acrylate, and N,N-diethylpropyl (meth)acrylate.

[0019] As a preferred embodiment of the above technical solution, the acid value of the alkali-soluble resin is 100-300 mg KOH / g, the average molecular weight is 30,000-150,000, and the addition amount is 50-65 parts by mass.

[0020] As a preferred embodiment of the above technical solution, the acid value of the alkali-soluble resin is 120 to 200 mg KOH / g.

[0021] As a preferred embodiment of the above technical solution, the photopolymerizable monomer is selected from one or more of nonylphenol (meth)acrylate, ethoxylated (propoxylated) nonylphenol (meth)acrylate, bisphenol A di(meth)acrylate, ethoxylated (propoxylated) bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol-propylene glycol di(meth)acrylate, and polyurethane acrylate oligomers.

[0022] As a preferred embodiment of the above technical solution, the amount of the photopolymerizable monomer added is 30-45 parts by mass.

[0023] As a preferred embodiment of the above technical solution, the photoinitiator is selected from at least one of the following compounds: 2,4,5-triaryl imidazole dimer and its derivatives, tetraethyl Michler's ketone, N-phenylglycine, acridine compounds, pyrazoline compounds, coumarin compounds, and thiol compounds.

[0024] 2,4,5-triaryl imidazole dimers and their derivatives include: 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0025] Examples of the acridine derivative include 9-phenylacridine, 9-(p-methylphenyl)acridine, 9-(p-ethylphenyl)acridine, 9-(p-propylphenyl)acridine, 9-(p-isopropylphenyl)acridine, 9-(p-n-butylphenyl)acridine, 9-(p-tert-butylphenyl)acridine, 9-(p-methoxyphenyl)acridine, 9-(p-ethoxyphenyl)acridine, 9-(p-propyloxyphenyl)acridine, 9-(p-aminophenyl)acridine, 9-(p-dimethylaminophenyl)acridine, 9-(p-diethylaminophenyl)acridine, 9-(p-chlorophenyl)acridine, 9-(p ...methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methylphenyl)acridine, 9-(p-methyl -(p-bromophenyl)acridine, 9-(p-carboxyphenyl)acridine, 9-(m-methylphenyl)acridine, 9-(m-n-propylphenyl)acridine, 9-(m-isopropylphenyl)acridine, 9-(m-n-butylphenyl)acridine, 9-(m-tert-butylphenyl)acridine, 9-(m-methoxyphenyl)acridine, 9-(m-ethoxyphenyl)acridine, 9-(m-propoxyphenyl)acridine, 9-(m-aminophenyl)acridine, 9-(m-dimethylaminophenyl)acridine, 9-(m-diethylaminophenyl)acridine, 9-(m-chlorophenyl)acridine and 9-(m-bromophenyl)acridine, etc.

[0026] Examples of the pyrazoline compound include 1-phenyl-3-(4-methoxyphenylvinyl)-5-(4-methoxyphenyl)-pyrazoline and phenyl-3-(4-isopropylphenylvinyl)-5-(4-isopropylphenyl)-pyrazoline.

[0027] Thiol compounds include hexanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithioacrylate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, tris(2-hydroxyethyl)isocyanurate-tris(mercaptopropionate), diethanolamine-tris(mercaptopropionate), diethylene glycol-bis(mercaptopropionate), and benzylmercaptopropionate.

[0028] As a preferred embodiment of the above technical solution, the amount of the photoinitiator added is 0.5-5 parts by mass.

[0029] Another object of the present invention is to provide a resist laminate.

[0030] A resist laminate comprises a support film, a polymer cover film and a resist layer arranged between the support film and the polymer cover film. The resist layer is formed by coating any one of the above-mentioned photosensitive resist compositions on the surface of the support film and drying the coating.

[0031] The resist laminate of the present invention can be prepared by weighing the components of the above-mentioned photosensitive resist composition, dissolving them in an organic solvent according to the above-mentioned mass ratio to obtain a mixed solution, then coating the mixed solution on a colorless transparent support film, and drying it to obtain a resist film; then, laminating a polymer cover film for protecting the resist on top of the resist film to finally obtain a resist laminate (photosensitive dry film). Coating can be performed using a reverse roll coater, gravure coater, comma coater, curtain coater, etc.; drying can be performed using infrared drying, hot air drying, etc., with a drying temperature of 50 to 120°C and a drying time that can be adjusted according to the concentration of the solution and is generally 1 to 20 minutes.

[0032] The support film can be a film made of low-density polyethylene, high-density polyethylene, polypropylene, polyester, polyethylene terephthalate, polycarbonate, or polyarylate. To prevent moisture from affecting the physical properties and coating conditions of the resist composition, the support film is preferably a polyethylene terephthalate, polyethylene, or polypropylene film; polyethylene terephthalate film is more preferred. The thickness of the support film is 10 to 50 μm, preferably 10 to 30 μm. It is preferably a colorless, transparent polymer film.

[0033] The polymer cover film is a resin film with low moisture permeability and easy peeling, which can be transparent or opaque, preferably polyethylene terephthalate, polyethylene or polypropylene film, with a thickness of 5 to 100 μm.

[0034] In summary, the present invention has the following beneficial effects:

[0035] 1) Compared with the prior art, the resist composition described in the present application has a lower developer foam height during development;

[0036] 2) Furthermore, as a resist laminate (photosensitive dry film), the flow tendency of the resist layer during storage can be reduced, thereby enhancing storage stability. DETAILED DESCRIPTION

[0037] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. The embodiments of the present invention and all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] The present invention is described in detail below with reference to the examples. The raw materials used without indicating the manufacturer and specifications are conventional products that can be obtained commercially. The following examples are merely preferred implementation examples of the present invention and do not constitute a limitation on the scope of protection of the present invention.

[0039] In the examples of the present application, (meth)acrylate refers to acrylate and methacrylate, and ethoxylated (propoxylated) acrylate refers to ethoxylated acrylate and ethoxylated propoxylated hybrid acrylate.

[0040] The specific substances in each embodiment and comparative example are as follows:

[0041] Alkali-soluble resins A1 to A3 are prepared by a known solution polymerization method. The formulations and main technical indicators are as follows:

[0042] Alkali-soluble resin A1 (Mw = 45,000, acid value = 169.4 mgKOH / g, solid content = 40%): methacrylic acid / methyl methacrylate / styrene = 26 / 49 / 25 (weight ratio);

[0043] Soluble resin A2 (Mw = 70,000, acid value = 156.4 mgKOH / g, solid content = 40%): methacrylic acid / methyl methacrylate / butyl acrylate = 24 / 56 / 20 (weight ratio);

[0044] Soluble resin A3 (Mw = 110,000, acid value = 162.9 mgKOH / g, solid content = 40%): methacrylic acid / methyl methacrylate / butyl acrylate = 25 / 60 / 15 (weight ratio);

[0045] Photopolymerizable monomers:

[0046] B1: (6) ethoxylated (12) propoxylated dimethacrylate (strong electron);

[0047] B2: (10) ethoxylated bisphenol A diacrylate (Sartomer);

[0048] B3: (3) ethoxylated trimethylolpropane triacrylate (Sartomer);

[0049] Photoinitiator:

[0050] C1: 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole (strong electron)

[0051] C2:9-phenylacridine (Aladdin reagent)

[0052] C3: Tetraethyl Michler's ketone (Aldrich)

[0053] Nanosilica:

[0054] D1: AEROSIL R202 (specific surface area 100, Evonik Degussa);

[0055] D2: AEROSIL R974 (specific surface area 170, Evonik Degussa);

[0056] D3: AEROSIL R812 (specific surface area 260, Evonik Degussa);

[0057] D4: SIPERNAT D13 (specific surface area 85, Evonik Degussa);

[0058] Surfactants:

[0059] E1: polypropylene glycol (average molecular weight: 2000, Aladdin reagent);

[0060] E2: polyethylene oxide-polypropylene oxide block copolymer, BASF Pluronic17R2;

[0061] E3: sorbitan trioleate (Span 85);

[0062] E4: sorbitan monooleate (Span 80);

[0063] Other additives:

[0064] F1: Diamond Green (Aladdin);

[0065] F2: Leuco crystal violet (Aladdin);

[0066] According to the formulations in Tables 1 and 2 below, the components were mixed in proportion and then stirred thoroughly until completely dissolved to form a resist composition solution with a solid content of 47-50%. This was evenly coated on the surface of a PET film (15 μm thick) serving as a support film using a coating machine and baked in a 95°C oven for 6-8 minutes. Depending on the evaluation requirements, a dry film resist layer with a thickness of 25 μm or 38 μm was formed. Next, a polyethylene film with a thickness of 20 μm was applied as a protective layer to the surface, resulting in a three-layer photosensitive dry film.

[0067] Table 1 Formulations of the resist compositions of Examples 1 to 10 and Comparative Examples 1 to 3

[0068]

[0069]

[0070] Table 2 Formulations of the resist compositions of Examples 11 to 18 and Comparative Examples 4 to 6

[0071]

[0072]

[0073] The following describes the sample preparation methods (including film lamination, exposure, development, pattern plating, and film stripping) prepared in Examples 1 to 18 and Comparative Examples 1 to 6, the sample evaluation methods, and the evaluation results; the evaluation results are shown in Tables 3 and 4.

[0074]

Film

[0075] The film was laminated using Changzhou Changyao Electronics CYL-M25 with a pressure of 4 kg / cm2, a speed of 1 m / min, and a temperature of 110°C.

[0076]

exposure

[0077] After lamination, the sample was left to stand for more than 15 minutes and then exposed using a Zhisheng Technology M-552 parallel light exposure machine. A Stouffer 41-step exposure ruler was used to measure the number of exposure grids, which was controlled at 20 grids.

[0078]

development

[0079] After exposure, the sample was left to stand for more than 15 minutes, the developing temperature was 30°C, the pressure was 1.5 kg / cm2, the developer was a 1% wt sodium carbonate aqueous solution, the developing time was 2.0 times the minimum developing time, and the sample was washed with water and dried after development.

[0080]

Graphic plating

[0081] The electroplating solution uses Zhengtianwei copper sulfate and stannous sulfate system, copper is plated first and then tin is plated, as follows: acid degreasing (10% concentration, 10 min, 40°C) → water washing for 2 min → micro-etching for 1 min (sodium persulfate 60 g / L + concentrated sulfuric acid 20 ml / L) → water washing for 1 min → acid immersion for 1 min (10% sulfuric acid solution) → electroplating copper (current density 2ASD, temperature 22-27°C, time 60 min) → water washing for 1 min → acid immersion for 1 min (10% sulfuric acid solution) → electroplating tin (current density 1ASD, temperature 20-25°C, time 10 min).

[0082]

Removal of membrane

[0083] Alkaline film removal, the film removal liquid is NaOH, the film removal liquid concentration is 3wt%, the film removal temperature is 50℃, the pressure is 1.5Kg / cm2, the film removal time is 1.5-2.0 times the minimum film removal time, and the film is washed and dried after film removal.

[0084]

Resolution Evaluation

[0085] Expose and develop using a photomask with a line / space pattern of 10 / 10-100 / 100 μm, rinse and dry, and observe with a magnifying glass. The smaller the resolution value, the better the resolution of the dry film.

[0086]

Evaluation of adhesion

[0087] Expose and develop the film using a photomask with a pattern of constant line spacing and varying line widths, using Line / Space = n / 400 μm (n ranges from 15 to 51, increasing by 3 each time). After washing and drying, the film is observed using a magnifying glass. The smaller the adhesion value, the better the adhesion of the dry film.

[0088]

Evaluation of developer foam height

[0089] A small developer was built, and 18 g of dry film resist was added to 1 L of 1.0 wt% sodium carbonate solution. The water pump was turned on and circulated for 30 min at 30°C, and the foam height was recorded.

[0090] ◎: Foam height <15mm;

[0091] ○: Foam height 15-23mm;

[0092] △: Foam height is 23-30mm;

[0093] ×: Foam height > 30 mm;

[0094]

Evaluation of plating resistance

[0095] After film application, exposure, development, pattern electroplating, and film stripping, a scanning electron microscope (SEM) test is used to observe whether there is any plating phenomenon.

[0096] ○: No plating phenomenon;

[0097] △: Slight permeation phenomenon;

[0098] ×: severe permeation phenomenon;

[0099]

Evaluation of dry film porosity

[0100] After removing the protective PE film from the resist, the resulting resist laminate was laminated onto a porous plate covered with 7mm-diameter circular holes using a heated press roller. During exposure, the light was focused on an area 0.2mm wider than the hole diameter. After removing the PET support layer, the dry film was developed using a development time eight times the minimum. The hole-masking performance of the dry film was tested, with 100 holes tested each time, and the number of holes broken was counted.

[0101] ◎The number of holes per 100 holes is less than or equal to 2

[0102] ○The number of holes per 100 holes is greater than 2 and less than or equal to 5

[0103] △The number of holes per 100 holes is greater than 5

[0104]

Storage stability evaluation

[0105] Use a 3-inch smooth fiberglass core to rewind 200m of dry film at the same rewinding tension, wrap the roll of dry film with black plastic paper, and place it in a constant temperature and humidity chamber at room temperature (5-20℃) and 50℃ respectively. The relative humidity of both chambers is controlled at 40-65%. After a period of time, observe the glue flow at both ends of the dry film and express the results with numbers. The smaller the number, the better the storage stability of the dry film.

[0106] Storage at room temperature:

[0107] 1: No glue flow after 6 months of placement;

[0108] 2: Slight glue flow occurs after 6 months of storage;

[0109] 3: Slight glue flow occurs after 3 months of storage;

[0110] 4: Severe gum flow occurs after 3 months of placement;

[0111] Store in a constant temperature and humidity chamber at 50°C:

[0112] 1: No glue flow after 1 month of placement;

[0113] 2: Slight glue flow occurs after 1 month of storage;

[0114] 3: Slight glue flow occurs after 2 weeks of storage;

[0115] 4: Severe glue bleeding occurs after 2 weeks of storage.

[0116] Table 3 Evaluation results of the resist compositions of Examples 1 to 10 and Comparative Examples 1 to 3

[0117]

[0118] Table 4 Evaluation results of the resist compositions of Examples 11 to 18 and Comparative Examples 4 to 6

[0119]

[0120] From Tables 1 to 4, it can be seen that the results of the examples are substantially better than those of the comparative examples, especially in terms of foam height and storage stability. Specifically, the results are mainly from these two aspects:

[0121] First, the foam height.

[0122] Example 8 shows a △, which is worse than the other examples. The only difference in Example 8 is the selection of D4, which is SIPERNAT D13 (specific surface area 85, Evonik Degussa). It can be seen that when the specific surface area of ​​nano-silica decreases, the effect of suppressing foam height becomes worse. In Example 1, D1 and AEROSIL R202 (specific surface area 100, Evonik Degussa) are used alone, and the foam height is 15-23 mm, which basically meets the requirements. Examples 1-3 do not use surfactants, but use 0.005-0.095 nano-silica (specific surface area meets the requirements), which can control the foam height at an acceptable level. In Example 2, the nano-silica content is relatively low, only 0.05, so the suppression effect on foam height is not as good as that of Examples 1 and 3.

[0123] Comparative Examples 1 and 4 are also marked as ×, clearly failing to meet the requirements. The unique feature of Comparative Examples 1 and 4 is that no surfactant or nano-silicon dioxide was used. A comprehensive review of Examples 1-3 and Examples 11-13 shows that a trace amount of nano-silicon dioxide significantly controls foam height.

[0124] Secondly, storage stability.

[0125] Comparative Examples 4 and 5 showed a 4, showing severe gel flow after two weeks, clearly not meeting the requirements. The unique feature of Comparative Example 4 is that no surfactant or nano-silicon dioxide was used. A comprehensive review of Examples 11-13 shows that a trace amount of nano-silicon dioxide significantly improves storage stability. The good foam height in Comparative Example 5 is due to the surfactant also having a certain effect in controlling foam height.

[0126] Finally, there is the combined effect of foam height and storage stability.

[0127] Examples 4 to 7 simultaneously use 0.03 to 0.07 nano-silica (specific surface area meets the requirements) and a more preferred surfactant ratio (0.8 to 2.85), so that excellent performance is shown in both foam height and storage stability.

[0128] Examples 14 to 15 and 18 simultaneously used 0.05 to 0.06 nano-silica (the specific surface area met the requirements) and a more preferred surfactant ratio (1.6 to 2.3), resulting in excellent performance in both foam height and storage stability.

Claims

1. A resist composition comprising an alkali-soluble resin, a photopolymerizable monomer and a photoinitiator, characterized in that: The invention also includes nano-silicon dioxide, wherein the nano-silicon dioxide is added in an amount of 0.1 parts by mass based on the total mass of the alkali-soluble resin and the photopolymerizable monomer as 100 parts by mass; the alkali-soluble resin is a carboxyl-containing vinyl resin obtained by copolymerizing at least one unsaturated carboxylic acid and at least one vinyl compound; the photopolymerizable monomer is selected from nonylphenol (meth) acrylate, ethoxylated (propoxylated) nonylphenol (meth) acrylate, bisphenol A di (meth) acrylate, ethoxylated (propoxylated) bisphenol A di (meth) acrylate, trisphenol A di (meth) acrylate, trisphenol B ... One or more of hydroxymethylpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol-propylene glycol di(meth)acrylate, and polyurethane acrylate oligomers.

2. The resist composition according to claim 1, wherein: The nano-silicon dioxide has a specific surface area> 100m 2 / g。 3. The resist composition according to claim 1, wherein: The alkali-soluble resin is 50 to 65 parts by mass, the photopolymerizable monomer is 30 to 45 parts by mass, and the photoinitiator is 0.5 to 5.0 parts by mass.

4. The resist composition according to claim 1, wherein: The resist composition further includes a surfactant, and the surfactant is added in an amount of 0 to 3.0 parts by mass based on 100 parts by mass of the total alkali-soluble resin and the photopolymerizable monomer.

5. The resist composition according to claim 4, wherein: The surfactant is a nonionic surfactant.

6. The resist composition according to claim 5, wherein: The nonionic surfactant is selected from one or more of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene alkyl ester, polyoxyethylene ether, polyoxypropylene ether, polyoxyethylene-polyoxypropylene block copolymer, nonylphenol polyoxyethylene ether, polyoxyethylene alkyl alcohol amine, polyoxyethylene alkylamine, glyceryl monostearate, pentaerythritol ester, and sorbitan ester.

7. The resist composition according to claim 1, wherein: The photoinitiator is at least one selected from the following compounds: 2,4,5-triaryl imidazole dimer and its derivatives, tetraethyl Michler's ketone, N-phenylglycine, acridine compounds, pyrazoline compounds, coumarin compounds, and thiol compounds.

8. A resist laminate comprising a support film, a polymer cover film, and a resist layer disposed between the support film and the polymer cover film, characterized in that: The resist layer is formed by applying the resist composition according to any one of claims 1 to 7 on the surface of the support film and drying the coating.

Images