JP2020066667A - Protective film-forming composition - Google Patents

Abstract

To provide a novel protective film-forming composition.SOLUTION: A composition contains a polyvinylpyrrolidone resin, a solvent and a laser light absorbent.SELECTED DRAWING: None

Description

  The present invention relates to a novel composition for forming a protective film and the like.

  When processing a substrate (for example, glass, semiconductor wafer, resin molded product, etc.), a protective film is formed on the surface of the substrate to protect the non-processed part, and after processing, the protective film There is known a method of removing.

Such a method is used, for example, in the processing of semiconductor wafers.
A semiconductor wafer is a laminated body in which an insulating film and a functional film are laminated on the surface of a semiconductor substrate such as silicon. This semiconductor wafer is irradiated with laser light to form a groove, and then cut along the groove. By doing so, a semiconductor chip is manufactured.
However, when a semiconductor wafer is irradiated with a laser beam, the laser beam is absorbed by the semiconductor substrate, so that a melt or a thermal decomposition product of the semiconductor substrate is generated, and the melt or the thermal decomposition product is a deposit (debris). As a result, there is a problem that it adheres to the surface of a semiconductor wafer or a semiconductor chip.

  Under such circumstances, there is known a method (laser dicing) in which a protective film that can be removed by washing with water is formed on the surface of a semiconductor wafer, and a laser beam is applied to perform processing (laser dicing). By irradiating a laser beam through the protective film, the debris can be attached to the surface of the protective film and washed with water to remove the debris together with the protective film.

As an agent for forming such a protective film, for example, Patent Document 1 describes a protective film agent containing a water-soluble resin and a water-soluble laser light absorber having an absorbance in a specific range.
Note that Patent Document 1 does not disclose a specific protective film agent containing a polyvinylpyrrolidone resin.

Patent No. 4571850

  An object of the present invention is to provide a novel protective film forming composition.

  Another object of the present invention is to provide a protective film-forming composition that forms a protective film that can be efficiently removed.

  Another object of the present invention is to provide a composition for forming a protective film, which forms a protective film capable of efficiently removing deposits.

  Yet another object of the present invention is to provide a method of making such a composition.

  The present inventor has found that the protective film agent described in Examples of Patent Document 1 has poor coating properties and storage stability in some cases, although the reason is not clear.

  Among these, the present inventor, as a result of repeated studies to solve the above problems, paying attention to polyvinylpyrrolidone-based resin, a combination of polyvinylpyrrolidone-based resin, a solvent and a laser light absorber, in coating properties. The inventors have found that they are excellent, and have conducted intensive studies to complete the present invention.

That is, the present invention relates to the following inventions.
[1]
A protective film-forming composition comprising a polyvinylpyrrolidone-based resin, a solvent, and a laser light absorber.
[2]
The composition according to [1], wherein the polyvinyl pyrrolidone resin has a K value of K30 to K90.
[3]
The composition according to [1] or [2], wherein the content of metal impurities in the polyvinylpyrrolidone-based resin is 10 ppm or less.
[4]
The composition according to any one of [1] to [3], wherein the laser light absorber contains at least one selected from ferulic acid and a benzophenone-based ultraviolet absorber.
[5]
The composition according to [4], wherein the benzophenone-based ultraviolet absorber is polyhydroxybenzophenone.
[6]
The composition according to any one of [1] to [5], wherein the solvent contains a propylene glycol derivative.
[7]
The composition according to [6], wherein the propylene glycol derivative comprises propylene glycol monoalkyl ether.
[8]
The composition according to [7], wherein the propylene glycol monoalkyl ether contains at least one selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether.
[9]
The composition according to any one of [1] to [8], wherein the solvent contains a propylene glycol derivative and the laser light absorber contains ferulic acid.
[10]
The composition according to any one of [1] to [9], which is for semiconductor processing.
[11]
The composition according to any one of [1] to [10], which is used for semiconductor laser processing.
[12]
A method for producing the composition according to any one of [1] to [11], comprising a step of subjecting a mixed solution of the respective components to an ion exchange treatment.
[13]
A method for producing the composition according to any one of [1] to [11], comprising a step of filtering a mixed solution of each component with a filter having a pore size of 1 μm or less.

According to the present invention, a novel composition for forming a protective film can be provided.
With such a composition, it is possible to easily remove the formed protective film and the deposits generated during processing by washing with water.
Further, since the composition of the present invention has excellent coatability on a substrate and workability of the formed protective film, it can be efficiently processed on a substrate.
Moreover, since the composition of the present invention has excellent storage stability, it can exhibit the above properties even after long-term storage.

  And in this invention, the manufacturing method of the above composition can be provided.

(Composition)
The composition of the present invention usually contains a polyvinylpyrrolidone-based resin, a solvent and a laser light absorber. The composition of the present invention can be used especially for forming a protective film.

(Polyvinylpyrrolidone resin)
The polyvinylpyrrolidone-based resin (sometimes referred to as PVP-based resin, PVP, etc.) is usually an N-vinyl-2-pyrrolidone-based polymer (a polymer containing at least N-vinyl-2-pyrrolidone as a polymerization component).
The PVP-based resin may have an N-vinyl-2-pyrrolidone unit, and may be derived from another monomer (a monomer copolymerizable with N-vinyl-2-pyrrolidone) if necessary. It may have a unit (may be modified with another monomer).

Other monomers are not particularly limited, and include, for example, α-olefins (for example, ethylene, propylene, etc.), (meth) acrylic acid esters [for example, methyl (meth) acrylate, (meth) acrylic acid. Ethyl, butyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl and other (meth) acrylic acid alkyl esters], unsaturated amides [eg (meth) acrylamide, diacetone acrylamide, N-methylol acrylamide, etc.] , Unsaturated acids {eg, unsaturated acids [eg (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, etc.], unsaturated acid esters [unsaturated acid esters other than (meth) acrylic acid, For example, alkyl (methyl, ethyl, propyl, etc.) esters, etc.], unsaturated acid anhydrides (maleic anhydride Acid etc.), salts of unsaturated acids [eg alkali metal salts (eg sodium salts, potassium salts etc.), ammonium salts etc.]}, glycidyl group-containing monomers [eg allyl glycidyl ether, glycidyl (meth) Acrylate, etc.], sulfonic acid group-containing monomer (eg, 2-acrylamido-2-methylpropanesulfonic acid, salts thereof, etc.), phosphoric acid group-containing monomer [eg, acid phosphooxyethyl (meth) acrylate, acid Phosphooxypropyl (meth) acrylate, etc.], vinyl ethers (eg, alkyl vinyl ethers), allyl alcohol, vinyl esters {eg, fatty acid vinyl esters [eg, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, caprylic acid] Vinyl, vinyl versatate, C _1-20 fatty acid vinyl ester such as monochlorovinyl acetate (for example, C _1-16 alkanoic acid-vinyl ester) and the like, aromatic carboxylic acid vinyl ester [for example, arene carboxylic acid vinyl ester such as vinyl benzoate (for example, C _7-12 arenecarboxylic acid-vinyl ester) and the like], etc., but the invention is not particularly limited thereto.
The other monomers may be used alone or in combination of two or more.

  You may use PVP type resin 1 type or in combination of 2 or more types.

  A commercially available product may be used as the PVP-based resin.

The method for producing the PVP-based resin is not particularly limited, and a known method may be used.
The PVP-based resin can be produced, for example, by synthesizing N-vinyl-2-pyrrolidone from acetylene, ammonia and formaldehyde, and polymerizing it in the presence of an oxidizing agent or the like.

  The K value of the PVP-based resin is not particularly limited, but is, for example, K12 to 120, preferably K20 to K100, and more preferably K30 to K90 from the viewpoint of efficiently removing the formed protective film.

  The K value of the PVP-based resin may be the K value according to the Fikentscher method. The method for measuring the K value is not particularly limited and may be measured according to a known method.

  The content of metal impurities (eg, Na, K, Fe, Cu, Ni, Cr, etc.) in the PVP-based resin is not particularly limited, but may be, for example, 20 ppm or less, preferably 10 ppm or less.

  The content of metal impurities in the PVP-based resin may be measured by a known method using ICP-MS (inductively coupled plasma mass spectrometry) or the like.

(solvent)
In the composition of the present invention, the solvent is not particularly limited, but water, alcohol (for example, monohydric alcohol (for example, methanol, ethanol, propanol, butanol), polyhydric alcohol (for example, ethylene glycol, diethylene glycol, propylene glycol). )}, Polyhydric alcohol derivative {eg, propylene glycol derivative [eg, propylene glycol monoalkyl ether (eg, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, etc. C _1-4 alkyl ether), propylene glycol monoalkyl ether acetate (eg, propylene glycol model). Nomyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, and other propylene glycol mono C _1-4 alkyl ether acetates)], ethylene glycol derivatives [eg, ethylene glycol monoalkyl ether (For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and other ethylene glycol mono C _1-4 alkyl ethers), ethylene glycol monoalkyl ether acetate (for example, ethylene glycol monomethyl ether) Acetate, ethylene glycol Ethyl ethylene glycol mono C _1-4 alkyl ether acetates such as ether acetate)]}, esters (e.g., methyl 3-methoxypropionate, ethyl 3-carboxylic acid alkyl ester such as ethoxyethyl propionate) and the like Can be mentioned.

  Among these solvents, water, propylene glycol derivatives and the like are preferable, water and propylene glycol monoalkyl ether and the like are more preferable, and water, propylene glycol monomethyl ether (hereinafter sometimes referred to as PGME), propylene glycol monoethyl ether and propylene. Particularly preferred are glycol monopropyl ether and propylene glycol monobutyl ether.

  The solvent may be used alone or in combination of two or more.

(Laser light absorber)
The laser light absorber is not particularly limited, and examples thereof include an ultraviolet absorber and a dye, and water-soluble ones are preferable.

  Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers {for example, polyhydroxybenzophenone (eg, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone. , 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone)}, a benzotriazole-based ultraviolet absorber (for example, 2,2'-methylenebis [6- (benzotriazol-2-yl) -4) -Tert-octylphenol]), ferulic acid and the like.

  Examples of the pigment include food additive pigments (for example, food red pigment (for example, food red No. 2, food red No. 40, food red No. 102, food red No. 104, food red No. 105, food red No. 106), Food yellow pigments (for example, food yellow NY, food yellow No. 4 tartrazine, food yellow No. 5), food blue pigments (for example food blue No. 1, food blue No. 2), food green pigments (for example food green No. 3) } Etc. are mentioned.

  Among these UV absorbers, benzophenone-based UV absorbers, ferulic acid and the like are preferable, and polyhydroxybenzophenone and ferulic acid are particularly preferable.

  The laser light absorbers may be used alone or in combination of two or more.

(Other ingredients)
The composition of the present invention may contain other components in addition to the polyvinylpyrrolidone resin, the solvent and the laser light absorber.

Other components are not particularly limited, and examples thereof include additives such as plasticizers, basic compounds [eg, ammonia, quaternary ammonium hydroxide {eg, tetraalkylammonium hydroxide (eg, tetramethylammonium hydroxide, , Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, etc. tetra C _1-8 alkylammonium hydroxide)}], and polyvinylpyrrolidone-based resins other than Water-soluble polymer (eg, polyvinyl alcohol resin, polyethylene glycol, polyethylene oxide, cellulose derivative (eg, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, etc.), polyglycerin (example If, diglycerol, positive real country all such triglycerol), polyacrylic acid and block copolymers (e.g., polyvinyl alcohol polyacrylic acid block copolymer), etc.} and the like.

  Other components may be used alone or in combination of two or more.

(Aspect of composition)
In the composition, the ratio of the PVP-based resin (the ratio of the PVP-based resin to the entire composition) is not particularly limited, but is, for example, 1 to 30 mass% (e.g., 5 to 30 mass%), preferably 1 to 25 mass. % (For example, 5 to 25% by mass), more preferably 1 to 20% by mass (for example, 5 to 20% by mass), and 1 to 15% by mass.

  In the composition, the ratio of the solvent (ratio of the solvent to the entire composition) is not particularly limited, but is, for example, 50 to 99% by mass (e.g., 50 to 95% by mass), preferably 60 to 99% by mass (e.g., 60 to 95% by mass), more preferably 70 to 99% by mass (for example, 70 to 95% by mass).

  In particular, when the solvent contains water and a propylene glycol derivative, the ratio of water to the propylene glycol derivative in the solvent is preferably 9: 1 to 1: 9, and water: propylene glycol derivative (mass ratio) is preferably 9: 1. To 2: 8 are more preferable, and 9: 1 to 3: 7 (for example, 9: 1 to 4: 6) are particularly preferable.

  In the composition, the ratio of the laser light absorber (the ratio of the laser light absorber to the entire composition) is not particularly limited, but is, for example, 0.01 to 5% by mass (e.g., 0.01 to 3% by mass), It may be preferably 0.01 to 1% by mass (for example, 0.01 to 0.5% by mass), and more preferably 0.05 to 0.5% by mass.

  When the composition contains other components, the ratio of the other components in the composition (ratio of the other components to the entire composition) is not particularly limited, but is, for example, 0.01 to 30% by mass, preferably 0. It may be 0.01 to 20% by mass, more preferably 0.01 to 10% by mass.

  In the composition, the ratio of the PVP resin and the solvent is not particularly limited, but the PVP resin: solvent (mass ratio) is, for example, 1:99 to 40:60 (for example, 5:95 to 30:70). , Preferably 1:99 to 25:75 (for example, 5:95 to 25:75), and more preferably 5:95 to 20:80.

  In the composition, the ratio of the PVP-based resin and the laser light absorbent is not particularly limited, but the laser light-absorbent is, for example, 0.01 to 20 parts by mass with respect to 100 parts by mass of the PVP-based resin (for example, 0.05 to 15 parts by mass), preferably 0.01 to 10 parts by mass (eg, 0.05 to 10 parts by mass, 0.1 to 10 parts by mass, 0.1 to 8 parts by mass). .

  When the composition contains other components, the ratio of the PVP-based resin to the other components in the composition is not particularly limited, but the other components may be, for example, 0. The amount may be 01 to 20 parts by mass, preferably 0.01 to 10 parts by mass.

  The viscosity of the composition of the present invention can be appropriately selected depending on the use of the composition and is not particularly limited. For example, the viscosity at 200 ° C. measured using a B-type rotational viscometer is, for example, 10 to 800 mPa · s. s, preferably 20 to 700 mPa · s.

The composition may have an absorbance at the absorption wavelength of laser light in a range not too high or too low.
For example, the composition is, for example, 0.1 to 0.9 abs, preferably, from the viewpoint that the absorbance at 355 nm of an aqueous solution diluted 100 times with water can reduce peeling around the processed (in particular, laser processed) portion. It may be 0.2 to 0.8 abs, more preferably 0.2 to 0.7 abs.
The absorbance of the composition can be adjusted by the types of the laser light absorber and the water-soluble polymer, the content ratio thereof, and the like. Particularly, according to the PVP-based resin used in the present invention, it is easy to adjust the absorbance within the above range.
The absorbance may be measured, for example, by the method described in Examples below.

(Method for producing composition)
The method for producing the composition is not particularly limited, but, for example, a polyvinylpyrrolidone-based resin, a solvent, and a laser light absorber (and, if necessary, other components) may be mixed. The mixing may be performed at room temperature or while heating. Further, the mixing may be performed with stirring.
The order of addition of each component in the composition is not particularly limited.

  Further, as a preferred embodiment of the method for producing the composition, when a laser light absorber is used, from the viewpoint of solubility, for example, a solution obtained by dissolving the laser light absorber in a propylene glycol derivative is obtained, May be mixed with a separately prepared aqueous solution of a water-soluble polymer.

In the step of producing the composition, the composition may be subjected to an ion exchange treatment.
In the ion exchange treatment of the composition, each component contained in the composition may be subjected to an ion exchange treatment, or a mixed liquid of each component may be subjected to an ion exchange treatment.
The ion exchange treatment method is not particularly limited, but for example, an ion exchange resin (for example, a cation exchange resin, an anion exchange resin, or a mixed ion exchange resin containing a cation exchange resin and an anion exchange resin) is filled. Alternatively, the mixture may be passed through the column.

Further, in the process of producing the composition, a mixed liquid of each component contained in the composition may be filtered.
The filtration method is not particularly limited, and for example, a filter may be used for filtration.
The filter is not particularly limited and may be appropriately selected depending on the application of the composition.
The pore size of the filter may be, for example, 10 μm or less, preferably 1 μm or less.

  When a basic compound is used as the other component in the composition, the pH of the composition can be adjusted by adding the basic compound to the mixed solution that has been subjected to the above-mentioned ion exchange treatment or filtration. The pH may be adjusted to a suitable value.

(Protective film)
A protective film can be formed by applying the composition of the present invention to the surface of a substrate.

  The substrate is not particularly limited, and examples thereof include glass, synthetic quartz, resin molded products, semiconductors (for example, semiconductor wafers), and the like.

  The coating method is not particularly limited and may be appropriately selected depending on the type of the base material. For example, spin coater method, screen printing method, comma coater method, bar coater method, die coater method, gravure coater method, etc. Is mentioned.

  The thickness of the protective film is not particularly limited and may be appropriately selected depending on the application of the composition, but is, for example, 0.01 to 50 μm (for example, 0.01 to 30 μm), preferably 0.01 to 20 μm. (For example, 0.01 to 15 μm), and more preferably 0.01 to 10 μm.

(Use of the composition)
By processing the base material through the protective film formed on the surface of the base material as described above, the base material can be processed in a state where the unprocessed portion is protected.

  The processing method is not particularly limited and can be appropriately selected depending on the type of the base material, and examples thereof include mechanical processing (for example, cutting processing, grinding processing), laser processing (for example, laser dicing), and the like.

  In particular, when laser processing is performed, the wavelength of laser light may be, for example, 355 nm or 532 nm. The wavelength of the laser light may be the absorption wavelength of the laser light absorber.

After performing the above processing, the protective film can be removed by washing the protective film.
The washing method is not particularly limited, but the protective film formed from the composition of the present invention can be efficiently removed by washing with water {eg, water, warm water (eg, warm water at 40 to 90 ° C.)}.
Further, by cleaning the protective film in this way, it is possible to efficiently remove deposits (for example, melts and pyrolysates) generated during processing.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

(Preparation of composition)
A liquid in which a water-soluble polymer, a solvent and a laser light absorber were mixed so as to have the respective compositions shown in Table 1 and Table 3 described below was heated at 90 ° C. for 1 hour while stirring to give the water-soluble polymer and The laser light absorber was dissolved in the solvent.
The water-soluble polymers shown in Tables 1 and 3 were as follows.
PVA-1: Japan Vinegar Poval JP-03 (saponification degree 88 mol%, degree of polymerization 300, sodium acetate 0.7 wt% (concentration of sodium 1963 ppm)
PVA-2: PVP-18 made by Nippon Viet Nam Poval (saponification degree 88 mol%, degree of polymerization 1800, sodium less than 1 ppm PVP-1: Wako Pure Chemical Industries PVP K-30 (K value 30)
PVP-2: PVP K-90 (K value 90) manufactured by Wako Pure Chemical Industries, Ltd.

The content of metal impurities (Na, K, Fe, Cu, Ni, Cr) in the PVP was measured by the ICP-MS method.
The content of metal impurities was as follows.
PVP-1: Na 1.1 ppm, K 0.2 ppm, Fe 0.1 ppm, Cu 0.1 ppm, Ni less than 0.1 ppm, Cr less than 0.1 ppm PVP-2: Na 0.1 ppm, K 0.2 ppm, Fe Less than 0.1 ppm, Cu less than 0.1 ppm, Ni less than 0.1 ppm, Cr less than 0.1 ppm

The solution dissolved as described above was cooled to room temperature, placed in a stock solution tank, and pumped from the stock solution tank to remove the cation exchange resin (Organo Amber-JET 1024 (H) -HG). After passing through the packed column and then through a filtration filter (Advantech Co., Ltd., pore size 1 μm PP filter (model number: MCP-JX-D10S)) and returning to the stock solution tank, ion exchange treatment and filtration treatment are performed. It was circulated for a time to obtain a purified composition.
In addition, at the time of passing through the column, in order not to change the composition of the composition, after discarding the first-flow liquid (the liquid that first came out at the time of passing) twice the volume of the resin packed in the column, Circulation treatment was performed.

(355 nm absorbance)
The absorption spectrum of an aqueous solution obtained by diluting the composition 100 times with ultrapure water was measured. The absorbance at 355 nm is shown in Table 1. The absorption spectrum was measured using an ultraviolet-visible spectrophotometer V-750 manufactured by Jusco Engineering Co., Ltd. with an optical path length of 1 cm.

(Spin coating)
Each composition was dropped onto the mirror surface side of a silicon semiconductor mirror wafer having a diameter of 6 inches, and spin coating conditions (dropping amount, rotation speed, holding time, spin cup) so that the film thickness was 0.5 to 1.5 μm. Was adjusted to form a protective film.

(Laser processing)
Laser processing was performed on the protective film surface side of the semiconductor mirror wafer using a laser processing machine with the following specifications.
Laser light source: YVO4 laser Wavelength: 355 nm
Repetition frequency: 50 to 100 kHz
Output: 0.3-4.0W
Focus spot size: φ9.2 μm
Processing feed rate: 1 to 800 mm / sec

(Washing with water)
Spin cleaning was performed while flowing cold water at 20 ° C. for 60 seconds on the protective film coated surface of the semiconductor mirror wafer after the laser processing.

  For each composition, coatability, laser processability, coating film residue after washing with water, and debris after washing with water were evaluated according to the following evaluation criteria.

(Applicability)
It was visually evaluated as follows.
◯: In-plane uniform coating was possible.
Δ: Radial streaks and coating unevenness were slightly observed, but the coating was almost uniform in the plane.
X: Radial streaks and coating unevenness were severely generated, and the coating could not be performed uniformly in the plane.

(Laser processability)
The peeling around the laser processable portion of the semiconductor mirror wafer was visually evaluated as follows.
○: No peeling around the processed part.
Δ: There was some peeling around the processed part.
X: There is obvious peeling around the processed part.

(Coating residue after washing with water)
It was visually evaluated as follows.
◯: The coating film was removed cleanly after washing with water.
Δ: After washing with water, there was a portion where the coating film was not removed and remained.
X: After washing with water, the coating film was hardly dissolved and remained on the entire surface.

(Debris after washing with water)
After washing with water, the periphery of the laser-processed portion of the semiconductor mirror wafer was observed with a laser microscope (VK-X200 manufactured by Keyence Corporation, objective lens magnification 150 times), and evaluated as follows.
◯: No adhesion of debris was observed after washing with water.
Δ: After washing with water, some debris was observed to be attached to the portion where the coating film remained.
X: Debris adhesion was observed after washing with water.

Table 2 shows the results of evaluating the compositions of Examples and Reference Examples as described above.
Table 2 shows the results of visual evaluation of the appearance of each composition and the results of evaluating the physical properties after storage by filling each composition with polypropylene bottles, sealing the bottles, and storing at 65 ° C for 6 months.

As Table 2 shows, the composition of the Example was excellent in coating property.
Moreover, the protective film formed of the composition of the example was excellent in processability.
Then, in the example, the protective film and debris could be cleanly removed by washing with water.

  On the other hand, the compositions of Reference Examples 1 and 2 had poor coatability, and the composition of Reference Example 2 showed turbidity.

  In addition, the compositions of Examples had excellent storage stability, whereas the compositions of Reference Examples 1 and 2 had poor storage stability and could form a protective film after long-term storage at high temperature. There wasn't.

  Further, with respect to the composition having the composition shown in Table 3 below, it is filled in a polypropylene bottle, sealed, stored at 65 ° C. for 6 months, and evaluated for physical properties after storage.

  As shown in Table 4, the compositions of Reference Examples 3 to 6 could not form a protective film after long-term storage at high temperature.

  Since the composition of the present invention is excellent in coating properties on a substrate, the substrate having a protective film formed on the surface thereof can be efficiently processed, and is industrially very useful.

Claims (13)

  A protective film-forming composition comprising a polyvinylpyrrolidone-based resin, a solvent, and a laser light absorber.   The composition according to claim 1, wherein the polyvinyl pyrrolidone resin has a K value of K30 to K90.   The composition according to claim 1 or 2, wherein the content of metal impurities in the polyvinylpyrrolidone resin is 10 ppm or less.   The composition according to any one of claims 1 to 3, wherein the laser light absorber comprises at least one selected from ferulic acid and a benzophenone-based ultraviolet absorber.   The composition according to claim 4, wherein the benzophenone-based ultraviolet absorber is polyhydroxybenzophenone.   The composition according to claim 1, wherein the solvent comprises a propylene glycol derivative.   The composition according to claim 6, wherein the propylene glycol derivative comprises propylene glycol monoalkyl ether.   The composition according to claim 7, wherein the propylene glycol monoalkyl ether comprises at least one selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether.   The composition according to claim 1, wherein the solvent comprises a propylene glycol derivative, and the laser light absorber comprises ferulic acid.   The composition according to any one of claims 1 to 9, which is for semiconductor processing.   The composition according to claim 1, which is used for semiconductor laser processing.   It is a manufacturing method of the composition in any one of Claims 1-11, Comprising: The manufacturing method including the process of ion-exchange-treating the mixed liquid of each component.   It is a manufacturing method of the composition in any one of Claims 1-11, Comprising: The manufacturing method including the process of filtering the mixed liquid of each component with the filter whose pore diameter is 1 micrometer or less.