Composition for protecting surface and surface protective film

Abstract

This composition for protecting a surface includes a polymer (A) including a structural unit (a) derived from a (meth)acrylate (a) having an acid-decomposable group, and an acid generator (B) including at least one generator selected from a photoacid generator and a thermal acid generator. A product derived from the polymer (A) after acid decomposition of the acid decomposable group has a hydrophilic group.

Description

Surface protection composition and surface protection film

[0001] The present invention relates to a surface protective composition and a surface protective film.

[0002] Techniques relating to surface protection films used in the manufacture of electronic devices include those described in Patent Documents 1 and 2, for example.

[0003] Patent Document 1 describes a semiconductor processing tape that is a laminate of a water-soluble film containing a polymer compound with a weight-average molecular weight of 200,000 or more and a low-molecular compound with a molecular weight of 800 or less, and a surface protection tape that protects the circuit surface of a semiconductor wafer. Patent Document 1 also describes that it is possible to provide a semiconductor processing tape that can be removed by washing with unheated water while achieving both grooving resistance and wafer adhesion.

[0004] Patent Document 2 describes a surface protection composition for protecting at least one surface of a substrate, the surface protection composition including a polymer having a hydrophilic group in the molecule and a compound that generates an acid or a base upon at least one of heating and irradiation with active energy rays. Patent Document 2 also describes that a surface protection composition can be provided for forming a protective layer that covers and protects at least one surface of a substrate in an electronic component device to be manufactured, and then is relatively easily removed upon contact with a liquid containing water.

[0005] JP 2023-043723 A International Publication No. 2023 / 195445 A

[0006] The present invention provides a surface protection composition that is water-resistant and capable of forming a water-washable protective film after at least one treatment selected from light irradiation and heating.

[0007] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result, have found that a surface protective composition can form a protective film that is water-resistant and can be washed with water after at least one treatment selected from light irradiation and heating, by combining a polymer (A) containing a structural unit (a) derived from a (meth)acrylate (a) having an acid-decomposable group with an acid generator (B) containing at least one selected from a photoacid generator and a thermal acid generator, and by acid-decomposing the acid-decomposable group into a product derived from the polymer (A) that has a hydrophilic group.

[0008] That is, according to the present invention, there are provided the following surface protection composition and surface protection film.

[0009] [1] A surface-protecting composition comprising: a polymer (A) containing a structural unit (a) derived from a (meth)acrylate (a) having an acid-decomposable group; and an acid generator (B) containing at least one selected from a photoacid generator and a thermal acid generator, wherein a product derived from the polymer (A) after acid decomposition of the acid-decomposable group has a hydrophilic group. [2] The surface-protecting composition according to [1], wherein a film comprising the surface-protecting composition does not peel off from a substrate, does not become cloudy, or does not dissolve when the following <Method 1> is performed. <Method 1> A film having a thickness of 10±5 μm comprising the surface-protecting composition is formed on a substrate, and then the substrate and the film are immersed in water for 10 minutes, and then the substrate and the film are removed from the water. [3] The surface-protecting composition according to [1] or [2], wherein the (meth)acrylate (a) contains a methacrylate. [4] The surface-protecting composition according to any one of [1] to [3], wherein the functional group protected by the acid-decomposable group comprises a carboxyl group. [5] The surface-protecting composition according to any one of [1] to [4], wherein the acid-decomposable group comprises a group containing an ether bond. [6] The surface-protecting composition according to [5], wherein the group containing an ether bond comprises an alkyl group having from 1 to 8 carbon atoms. [7] The surface-protecting composition according to [6], wherein the alkyl group is linear. [8] The surface-protecting composition according to any one of [1] to [7], wherein the polymer (A) further comprises structural units (b) derived from one or more monomers (b) selected from the group consisting of (meth)acrylic acid, (meth)acrylamide, and (meth)acrylates containing an ether bond. [9] The surface-protecting composition according to any one of [1] to [8], wherein the weight-average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography in terms of polystyrene is from 5,000 to 10,000,000.

[10] The surface protecting composition according to any one of [1] to [9], wherein the acid generator (B) comprises a photoacid generator.

[11] The surface protecting composition according to

[10] , wherein the photoacid generator comprises one or two selected from the group consisting of a sulfonium salt-type photoacid generator, an iodonium salt-type photoacid generator, and a non-ionic photoacid generator.

[12] The composition for protecting a surface according to any one of [1] to

[11] , wherein the content of the acid generator (B) is 1.0 part by mass or more and 50 parts by mass or less relative to 100 parts by mass of the polymer (A).

[13] A surface protective film comprising the composition for protecting a surface according to any one of [1] to

[12] .

[0010] According to the present invention, it is possible to provide a surface protection composition that is water-resistant and capable of forming a protective film that can be washed off with water after at least one treatment selected from light irradiation and heating.

[0011] Hereinafter, embodiments of the present invention will be described. In this specification, unless otherwise specified, "A to B" indicating a range of numerical values ​​means A or more and B or less.

[0012] <Surface Protecting Composition> The surface protecting composition of this embodiment includes a polymer (A) including a structural unit (a) derived from a (meth)acrylate (a) having an acid-decomposable group, and an acid generator (B) including at least one selected from a photoacid generator and a thermal acid generator, and a product derived from the polymer (A) after acid decomposition of the acid-decomposable group has a hydrophilic group.

[0013] The surface protective composition of this embodiment contains a polymer (A) containing a structural unit (a) derived from a (meth)acrylate (a), thereby providing a film formed from the surface protective composition with water resistance. Furthermore, the surface protective composition contains a polymer (A) containing a structural unit (a) derived from a (meth)acrylate (a) having an acid-decomposable group, and an acid generator (B) containing at least one selected from a photoacid generator and a thermal acid generator. When the film formed from the surface protective composition is subjected to at least one treatment selected from light irradiation and heating, the acid generator (B) generates an acid, which deprotects, i.e., acid-decomposes, the acid-decomposable group of the polymer (A). Furthermore, the product derived from the polymer (A) after acid decomposition of the acid-decomposable group contains a hydrophilic group, thereby improving the hydrophilicity of the film formed from the surface protective composition and enabling water washing of the surface protective film. The product derived from the polymer (A) after acid decomposition of the acid-decomposable group refers to the polymer (A) after the acid-decomposable group has been eliminated by acid decomposition.

[0014] The hydrophilic groups in the product derived from polymer (A) after acid decomposition of the acid-decomposable groups in polymer (A) preferably contain one or more selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups, sulfonyl groups, and thiol groups, more preferably one or more selected from the group consisting of hydroxyl groups and carboxyl groups, and even more preferably carboxyl groups, which further improves water washability after at least one treatment selected from light irradiation and heating.

[0015] (Polymer (A)) The polymer (A) in the surface protective composition of this embodiment contains a structural unit (a) derived from a (meth)acrylate (a) having an acid-decomposable group. The polymer (A) containing the structural unit (a) derived from the (meth)acrylate (a) improves the water resistance of a film formed from the surface protective composition. Furthermore, the polymer (A) containing an acid-decomposable group means that when the acid generator (B) generates an acid after at least one treatment selected from light irradiation and heating, the acid-decomposable group of the polymer (A) is acid-decomposed by the acid, and the product derived from the polymer (A) after acid decomposition of the acid-decomposable group contains a hydrophilic group, improving the hydrophilicity of the film formed from the surface protective composition and enabling the film to be washed with water.

[0016] The (meth)acrylate (a) in the structural unit (a) of the polymer (A) preferably contains methacrylate, which improves the water washability and coatability of the resulting film while maintaining the water resistance of the resulting film.

[0017] The functional group in the polymer (A) protected by the acid-decomposable group preferably contains a carboxyl group, from the viewpoint of further improving the balance of performance between water washability and water resistance.

[0018] The acid-decomposable group in polymer (A) preferably comprises a group containing an ether bond.Therefore, after at least one treatment selected from light irradiation and heating, the acid-decomposable group is more reliably deprotected, and the water washability of the obtained film is further improved.The group containing an ether bond, from the viewpoint of further improving the water washability of the obtained film, preferably comprises one or more selected from the group consisting of ethoxyethyl group, propoxyethyl group, isopropoxyethyl group, butoxyethyl group, isobutoxyethyl group, (cyclohexyloxy) ethyl group and tetrahydropyranyl group, more preferably comprises one or more selected from the group consisting of ethoxyethyl group, propoxyethyl group, isopropoxyethyl group, butoxyethyl group and tetrahydropyranyl group, still more preferably comprises one or more selected from the group consisting of ethoxyethyl group, propoxyethyl group, isopropoxyethyl group and butoxyethyl group, still more preferably comprises one or more selected from the group consisting of ethoxyethyl group, isopropoxyethyl group and butoxyethyl group.

[0019] Furthermore, from the viewpoint of further improving the water washability of the resulting membrane, the group containing an ether bond preferably contains an alkylene group having 1 to 4 carbon atoms, more preferably contains an alkylene group having 1 to 3 carbon atoms, even more preferably contains an alkylene group having 1 to 2 carbon atoms, still more preferably contains an ethylene group, and even more preferably contains a 1,1-ethylene group.

[0020] From the viewpoint of further improving the water washability of the resulting membrane, the group containing an ether bond preferably contains an alkyl group having from 1 to 8 carbon atoms, more preferably contains an alkyl group having from 1 to 7 carbon atoms, even more preferably contains an alkyl group having from 1 to 6 carbon atoms, even more preferably contains an alkyl group having from 1 to 5 carbon atoms, even more preferably contains an alkyl group having from 1 to 4 carbon atoms, and even more preferably contains an alkyl group having from 1 to 3 carbon atoms. Furthermore, when the group containing an ether bond contains an alkyl group having from 1 to 8 carbon atoms, the alkyl group is preferably linear, from the viewpoint of further improving the water washability of the resulting membrane.

[0021] In addition to the structural unit (a), the polymer (A) preferably further contains structural units (b) derived from one or more monomers (b) selected from the group consisting of (meth)acrylic acid, (meth)acrylamide, and (meth)acrylates containing an ether bond. The monomer (b) more preferably contains (meth)acrylic acid. The (meth)acrylate containing an ether bond preferably includes one or more selected from the group consisting of acryloylmorpholine, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, and 2-[2-(2-methoxyethoxy)ethoxy]ethyl acrylate. When the polymer (A) further contains the structural unit (b), the resulting film has improved adhesion to substrates and water resistance. Furthermore, the coatability of the surface protection composition is improved. Furthermore, when the monomer (b) forming the structural unit (b) contains (meth)acrylic acid, the water resistance of the resulting film can be maintained while further improving the balance of film-forming properties and adhesion.

[0022] When polymer (A) further comprises the structural unit (b) derived from monomer (b), the content of structural unit (b) is, when the total content of structural unit in polymer (A) is 100 mol%, preferably 0 mol% or more and 50 mol% or less, more preferably 0 mol% or more and 40 mol% or less, more preferably 0 mol% or more and 35 mol% or less, more preferably 0 mol% or more and 30 mol% or less, more preferably 0 mol% or more and 20 mol% or less, more preferably 0 mol% or more and 10 mol% or less, more preferably 0 mol% or more and 5 mol% or less.By the content of structural unit (b) being within the above-mentioned range, while maintaining the water resistance of the film obtained, the performance balance of coating property and adhesion can be further improved.

[0023] The weight average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography in terms of polystyrene is preferably 5,000 to 10,000,000, more preferably 10,000 to 5,000,000, even more preferably 15,000 to 1,000,000, even more preferably 20,000 to 500,000, even more preferably 25,000 to 200,000, and even more preferably 35,000 to 200,000. When the weight average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography in terms of polystyrene is within the above range, the water washability of the resulting membrane can be further improved.

[0024] The Mw / Mn calculated from the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography of the polymer (A) is preferably 1.0 or more and 100 or less, more preferably 1.0 or more and 50 or less, even more preferably 1.5 or more and 30 or less, even more preferably 1.5 or more and 20 or less, even more preferably 2.0 or more and 15 or less, and even more preferably 2.5 or more and 10 or less. When the Mw / Mn calculated from the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography of the polymer (A) is within the above range, the water washability of the obtained membrane can be further improved.

[0025] The weight average molecular weight (Mw) and Mw / Mn of the polymer (A) in terms of polystyrene, measured by gel permeation chromatography, can be adjusted by appropriately adjusting conditions such as the type of catalyst, polymerization temperature, polymerization pressure, and polymerization time in the synthesis of the polymer (A) described below.

[0026] (Method for Synthesizing Polymer (A)) The polymer (A) of this embodiment can be synthesized by an appropriate known method. For example, the polymer (A) can be obtained by polymerizing the (meth)acrylate (a) and monomer (b) having the acid-decomposable group described above in the presence of an appropriate known polymerization catalyst. The polymerization catalyst can be, for example, one or more selected from the group consisting of azo compounds, organic peroxides, and photopolymerization initiators. Examples of azo compounds that can be used include 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile). When an azo compound is used as the polymerization catalyst, the monomers can be polymerized by, for example, heating a solution containing the (meth)acrylate (a), monomer (b), and azo compound at 50 to 80°C for 1 hour to 50 hours. Examples of photopolymerization initiators that can be used include 1-hydroxycyclohexyl phenyl ketone and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. When a photopolymerization initiator is used as the polymerization catalyst, for example, a solution containing (meth)acrylate (a), monomer (b) and the photopolymerization initiator is irradiated with UVA light at a UV intensity of 20 to 50 mW / cm ２ The monomer can be polymerized by irradiating the solution with UV light at a temperature of about 1000 nm for about 1 to 60 minutes. As a commercially available organic peroxide, Perbutyl (registered trademark) O (manufactured by NOF Corporation) can be used.

[0027] (Acid Generator (B)) The acid generator (B) in the surface protecting composition of this embodiment includes at least one selected from a photoacid generator and a thermal acid generator, and from the viewpoint of further improving the water washability of the resulting film, the acid generator (B) preferably includes a photoacid generator.

[0028] The photoacid generator preferably contains one or more selected from sulfonium salt-type photoacid generators, iodonium salt-type photoacid generators, and nonionic photoacid generators, from the viewpoint of further improving the water resistance of the resulting film and further improving the water washability of the film after light irradiation, and more preferably contains a sulfonium salt-type photoacid generator, from the viewpoint of extending the wavelength of the irradiated light.

[0029] Examples of the thermal acid generator include aromatic sulfonium salts, aromatic iodonium salts, ammonium salts, aluminum chelates, and boron trifluoride amine complexes.

[0030] Here, the product other than the acid after acid generation by the acid generator (B) preferably has a molecular weight of 20 or more and 1,200 or less, more preferably 30 or more and 1,000 or less, even more preferably 50 or more and 800 or less, even more preferably 80 or more and 500 or less, even more preferably 100 or more and 350 or less, and even more preferably 120 or more and 300 or less.

[0031] The content of the acid generator (B) in the surface protective composition is preferably 1.0 part by mass or more and 50 parts by mass or less, more preferably 1.0 part by mass or more and 45 parts by mass or less, even more preferably 1.5 parts by mass or more and 40 parts by mass or less, even more preferably 2.0 parts by mass or more and 35 parts by mass or less, even more preferably 2.0 parts by mass or more and 30 parts by mass or less, even more preferably 2.5 parts by mass or more and 30 parts by mass or less, and even more preferably 3.0 parts by mass or more and 25 parts by mass or less, relative to 100 parts by mass of the polymer (A). When the content of the acid generator (B) in the surface protective composition is within the above range, the water washability of the obtained film can be further improved.

[0032] (Method for Producing the Surface Protective Composition) The method for producing the surface protective composition of this embodiment can be carried out by any known method. For example, the composition can be produced by mixing the polymer (A), acid generator (B), and solvent described above using a mixer rotor or the like until the mixture is homogeneous. As the solvent, one or more solvents selected from the group consisting of acetone, ethyl acetate, toluene, ethanol, propylene carbonate, 1-methoxy-2-propanol, and propylene glycol monomethyl ether acetate can be used. Only one solvent may be used, or two or more solvents may be used in combination.

[0033] (Formation of a film from the surface protective composition) The surface protective composition of this embodiment can be formed into a film by any known method. For example, the surface protective composition can be applied to a substrate such as a silicon wafer to a film thickness of about 10 to 120 μm, and then dried to form a film. Drying conditions are preferably at a temperature of 50° C. or higher and 130° C. or lower, more preferably at a temperature of 60° C. or higher and 100° C. or lower, and for a period of preferably 1 minute to 1 hour, more preferably 3 minutes to 30 minutes.

[0034] (Method for cleaning a film made of the surface protective composition) Cleaning of a film made of the surface protective composition of this embodiment (i.e., a surface protective film) is carried out as follows. When the acid generator (B) contains a photoacid generator, it is preferable to irradiate the film made of the surface protective composition of this embodiment formed on a substrate or the like with light. By irradiating with light, the film made of the surface protective composition can be dissolved, and water washability can be further improved. The light irradiation is specifically UV irradiation, and the illuminance is preferably 5 mW / cm. ２ More than 9000mW / cm ２ More preferably, the illuminance is 5 mW / cm or less. ２ More than 5000mW / cm ２ More preferably, the illuminance is 10 mW / cm or less. ２ More than 1000mW / cm ２ More preferably, the illuminance is 15 mW / cm or less. ２ More than 500mW / cm ２ The irradiation time is preferably 10 seconds or more and 300 seconds or less, more preferably 20 seconds or more and 200 seconds or less, and the integrated light amount is preferably 500 mJ / cm ２ More than 400J / cm ２ or less, more preferably 1000 mJ / cm ２ More than 300J / cm ２ More preferably, 1300 mJ / cm or less ２ More than 250J / cm ２Hereinafter, the ultraviolet irradiation is preferably performed under ultraviolet conditions with a wavelength of 200 nm or more and 400 nm or less, more preferably 250 nm or more and 380 nm or less. Light irradiation can be performed using, for example, an LED light or a high-pressure mercury lamp. As an LED light, for example, Hololite Kaku manufactured by Pi Photonics Co., Ltd. can be used. As a high-pressure mercury lamp, for example, UVC-408 manufactured by Technovision Co., Ltd. can be used. When the acid generator (B) contains a thermal acid generator, it is preferable to heat the film made of the surface protective composition of this embodiment formed on a substrate or the like. The heating temperature is preferably 100°C or more and 200°C or less, more preferably 120°C or more and 180°C or less, and even more preferably 140°C or more and 160°C or less. Furthermore, the heating time is preferably 1 minute or more and 30 minutes or less, more preferably 2 minutes or more and 15 minutes or less. When performing water washing, it is preferable to immerse the film made of the surface protective composition and the substrate or the like in water after light irradiation or heating as described above. In addition, the film made of the surface protection composition can also be water-cleaned by subjecting it to one or more cleaning methods selected from the group consisting of jet cleaning, two-fluid cleaning, spray cleaning, shower cleaning, and ultrasonic cleaning.

[0035] After water washing under the above conditions, it is preferable that the entire film made of the surface protective composition is dissolved. By dissolving the entire film made of the surface protective composition, it is possible to further prevent the film made of the surface protective composition from remaining on the substrate or the like after water washing. In addition, it becomes easier to treat wastewater when the film made of the surface protective composition is washed with water.

[0036] The water resistance of the surface protective composition of this embodiment is evaluated, for example, according to the following <Method 1>. <Method 1> A film of 10±5 μm thickness made of the surface protective composition of this embodiment is formed on a substrate, and then the substrate and film are immersed in water for 10 minutes. When the substrate and film are then removed from the water, it is preferable that the film made of the surface protective composition does not peel off from the substrate, does not become cloudy, or does not dissolve. A glass plate or a silicon wafer can be used as the substrate. This can further improve the water resistance of the film made of the surface protective composition.

[0037] The cleaning properties of the surface protection composition of this embodiment can be evaluated, for example, by the following <Method 2>. <Method 2> A film of 10±5 μm thickness made of the surface protection composition of this embodiment is formed on a substrate, and the film is placed on a SUS table and exposed to an illuminance of 20 mW / cm. ２ , irradiation time 70 seconds, cumulative light amount 1400 mJ / cm ２ The substrate and the film are then immersed in water, and the time required for the entire film to dissolve in water is defined as the dissolution time (minutes). A glass plate or a silicon wafer can be used as the substrate. When the above-described <Method 2> is performed, the dissolution time of the surface protective composition is preferably 30 minutes or less, more preferably 25 minutes or less, even more preferably 20 minutes or less, even more preferably 15 minutes or less, even more preferably 12 minutes or less, even more preferably 10 minutes or less, even more preferably 8 minutes or less, even more preferably 5 minutes or less, even more preferably 4 minutes or less, even more preferably 3 minutes or less, even more preferably 2 minutes or less, and even more preferably 1 minute or less, from the viewpoint of further improving water cleanability. There is no lower limit to the dissolution time of the surface protective composition, but it may be, for example, 10 seconds or more, or 20 seconds or more.

[0038] <Surface protective film> The surface protective film of this embodiment includes the surface protective composition of this embodiment. The surface protective film of this embodiment may be formed by applying the surface protective composition of this embodiment onto a substrate or the like to form a membrane, or may be formed as a film.

[0039] The surface protection film of this embodiment can be used as a surface protection film that protects the surface of electronic components and is ultimately removed in the manufacturing process of electronic devices. Examples of electronic components include semiconductor chips such as ICs, LSIs, discrete devices, light-emitting diodes, and light-receiving elements, as well as semiconductor panels, semiconductor packages, and wafers.

[0040] The thickness of the surface protective film of this embodiment is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more, from the viewpoint of further improving the performance balance between water resistance and surface protectiveness, and is preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less, from the viewpoint of further improving water washability.

[0041] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted.

[0042] The present invention is not limited to the above-described embodiment, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

[0043] The present embodiment will be described in detail below with reference to examples and comparative examples, but the present embodiment is not limited to the descriptions of these examples.

[0044] <Raw Materials> The raw materials used in the examples and comparative examples are shown below.

[0045] (Polymer (A)) ((Meth)acrylate (a) (Structural unit (a))) 1-ethoxyethyl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd. 1-propoxyethyl methacrylate 1-isopropoxyethyl methacrylate 1-butoxyethyl methacrylate 1-isobutoxyethyl methacrylate 1-(cyclohexyloxy)ethyl methacrylate 2-tetrahydropyranyl methacrylate 2-tetrahydropyranyl acrylate (Monomer (b) (Structural unit (b))) Acrylic acid: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Methacrylic acid: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Acryloylmorpholine: manufactured by Tokyo Chemical Industry Co., Ltd. (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate: MEDOL-10 manufactured by Osaka Organic Chemical Industry Ltd.

[0046] <Synthesis of Polymer (A)> According to the formulations in Table 1, polymer solutions of the respective examples were synthesized by the following method.

[0047] (Preparation of Polymer Solution 1) 0.04 g of 1-hydroxycyclohexyl phenyl ketone was added to 2.0 g of 1-ethoxyethyl methacrylate to obtain a monomer solution. This was irradiated with light for 1 hour under ice-cooling and stirring in a nitrogen atmosphere in accordance with the light irradiation method described below to obtain a polymer. Next, 4 g of acetone was added to the polymer, and the mixture was heated at 50°C for 3 hours with stirring to obtain Polymer Solution 1 containing an acrylic polymer. A mercury xenon lamp illumination device (manufactured by Hamamatsu Photonics KK, LC8:L9588) was used for light irradiation. The illumination intensity of the panel display was set to 23%, and the condenser lens was positioned 7 cm away from the monomer solution for irradiation. The intensity of the light irradiated to the monomer solution was measured using an illuminance meter (manufactured by EIT, UV PowerPuck II). When the illuminance meter and the mercury xenon lamp illumination device were positioned 7 cm apart, the UVA intensity was 28 mW / cm. ２ It was.

[0048] (Preparation of Polymer Solution 2) 3.0 g of 1-ethoxyethyl methacrylate and 5.8 g of ethyl acetate were mixed to obtain a monomer solution. Furthermore, 0.3 g of 2,2'-azobis(isobutyronitrile) (AIBN, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 6.0 g of ethyl acetate to obtain an initiator solution. Next, 0.69 mL of the initiator solution was added to the monomer solution heated to 65°C under a nitrogen atmosphere. This was heated for 1 hour under a nitrogen atmosphere with stirring, and then 0.69 mL of the initiator solution was added again, followed by heating for an additional 7 hours. This was allowed to cool to room temperature and allowed to stand for 14 hours or more, and then again heated for 7 hours under a nitrogen atmosphere with stirring at 65°C to obtain Polymer Solution 2 containing an acrylic polymer.

[0049] (Preparation of Polymer Solution 3) Polymer solution 3 containing an acrylic polymer was obtained in the same manner as polymer solution 2, except that the amount of 1-ethoxyethyl methacrylate in the monomer solution was changed to 5.0 g, the amount of ethyl acetate was changed to 10.7 g, and the amount of initiator solution added was changed to 0.58 mL each.

[0050] (Preparation of Polymer Solution 4) 5.0 g of 1-ethoxyethyl methacrylate and 4.8 g of ethyl acetate were mixed to obtain a monomer solution. Meanwhile, 0.3 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 6.0 g of ethyl acetate to obtain an initiator solution. Then, 0.1 mL of the initiator solution was added to the monomer solution heated to 51°C under a nitrogen atmosphere. This was heated for 1 hour under a nitrogen atmosphere with stirring, and then 0.1 mL of the initiator solution was added again, followed by heating for an additional 8 hours. This was allowed to cool to room temperature, allowed to stand for 14 hours or more, and then heated again under a nitrogen atmosphere with stirring at 51°C for 10 hours. This was allowed to cool to room temperature, allowed to stand for 14 hours or more, and then heated again under a nitrogen atmosphere with stirring at 51°C for 7 hours to obtain polymer solution 4 containing an acrylic polymer.

[0051] (Preparation of Polymer Solution 5) 8.0 g of 1-ethoxyethyl methacrylate, 1.2 g of acrylic acid, and 18 g of ethyl acetate were mixed to obtain a monomer solution. Furthermore, 0.37 g of 2,2'-azobis(isobutyronitrile) (AIBN, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 7.4 g of ethyl acetate to obtain an initiator solution. 2.1 mL of the above initiator solution was added to the monomer solution heated to 65°C under a nitrogen atmosphere. After heating these under a nitrogen atmosphere with stirring for 1 hour, 2.1 mL of the initiator solution was added again and heated for an additional 7 hours. After allowing to cool to room temperature and leaving to stand for 14 hours or more, it was again heated under a nitrogen atmosphere with stirring at 65°C for 7 hours to obtain Polymer Solution 5.

[0052] (Preparation of Polymer Solution 6) Polymer solution 6 containing an acrylic polymer was obtained in the same manner as polymer solution 5, except that the acrylic acid in the monomer solution was changed to 1.5 g of methacrylic acid and the amount of initiator solution added was changed to 2.2 mL each.

[0053] (Preparation of Polymer Solution 7) Polymer solution 7 containing an acrylic polymer was obtained in the same manner as polymer solution 5, except that the amount of 1-ethoxyethyl methacrylate in the monomer solution was changed to 4.0 g, the acrylic acid was changed to 1.2 g of acryloylmorpholine, and the amount of initiator solution added was changed to 1.2 mL each.

[0054] (Preparation of Polymer Solution 8) Polymer solution 8 containing an acrylic polymer was obtained in the same manner as polymer solution 5, except that the amount of 1-ethoxyethyl methacrylate in the monomer solution was changed to 4.0 g, the acrylic acid was changed to 0.84 g of MEDOL-10, and the amount of initiator solution added was changed to 1.1 mL each.

[0055] (Preparation of Polymer Solution 9) Polymer solution 9 containing an acrylic polymer was obtained in the same manner as polymer solution 2, except that the 1-ethoxyethyl methacrylate in the monomer solution was changed to 4.0 g of 1-propoxyethyl methacrylate, the amount of ethyl acetate was changed to 7.7 g, and the amount of initiator solution added was changed to 0.93 mL each.

[0056] (Preparation of Polymer Solution 10) A polymer solution 10 containing an acrylic polymer was obtained in the same manner as in polymer solution 2, except that the 1-ethoxyethyl methacrylate in the monomer solution was changed to 4.0 g of 1-isopropoxyethyl methacrylate, the amount of ethyl acetate was changed to 7.7 g, and the amount of initiator solution added was changed to 0.93 mL each.

[0057] (Preparation of Polymer Solution 11) A polymer solution 11 containing an acrylic polymer was obtained in the same manner as in Polymer Solution 2, except that the amount of 1-ethoxyethyl methacrylate in the monomer solution was changed to 4.0 g of 1-butoxyethyl methacrylate, the amount of ethyl acetate was changed to 7.7 g, and the amount of initiator solution added was changed to 0.93 mL each.

[0058] (Preparation of Polymer Solution 12) A polymer solution 12 containing an acrylic polymer was obtained in the same manner as in Polymer Solution 2, except that the amount of 1-ethoxyethyl methacrylate in the monomer solution was changed to 4.0 g of 1-isobutoxyethyl methacrylate, the amount of ethyl acetate was changed to 7.7 g, and the amount of initiator solution added was changed to 0.93 mL each.

[0059] (Preparation of Polymer Solution 13) A polymer solution 13 containing an acrylic polymer was obtained in the same manner as in polymer solution 2, except that the 1-ethoxyethyl methacrylate in the monomer solution was changed to 5.0 g of 1-(cyclohexyloxy)ethyl methacrylate, the amount of ethyl acetate was changed to 9.7 g, and the amount of initiator solution added was changed to 1.2 mL each.

[0060] (Preparation of Polymer Solution 14) A polymer solution 14 containing an acrylic polymer was obtained in the same manner as in polymer solution 2, except that the 1-ethoxyethyl methacrylate in the monomer solution was changed to 5.0 g of 2-tetrahydropyranyl methacrylate, the amount of ethyl acetate was changed to 9.7 g, and the amount of initiator solution added was changed to 1.2 mL each.

[0061] (Preparation of Polymer Solution 15) Polymer solution 15 containing an acrylic polymer was obtained in the same manner as polymer solution 2, except that 1-ethoxyethyl methacrylate in the monomer solution was changed to 5.0 g of 2-tetrahydropyranyl acrylate, ethyl acetate was changed to 9.7 g, and the amount of initiator solution added was changed to 1.2 mL each.

[0062] The following commercially available polymers (A) were used: Copolymer of 4-(1-ethoxyethoxy)styrene and 4-hydroxystyrene: WMWP-240H, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., CAS RN: 158593-28-3, 30% PGMEA solution; Polyvinyl alcohol: JMR-10L, manufactured by Japan Vinyl Acetate & Poval Co., Ltd.

[0063] (Acid Generator (B)) Non-ionic photoacid generator: Bis(tert-butylsulfonyl)diazomethane, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., WPAG-170 Sulfonium salt photoacid generator: CPI-110B, manufactured by San-Apro Co., Ltd. Sulfonium salt photoacid generator: CPI-100B, manufactured by San-Apro Co., Ltd. Iodonium salt photoacid generator: 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0064] <Weight Average Molecular Weight (Mw), Number Average Molecular Weight (Mn), and Mw / Mn> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer (A) in each example were measured by gel permeation chromatography (GPC) under the following conditions. Automatic injection device: 717plus, manufactured by Nihon Waters Pump: KP-22-13S dual pump, manufactured by Fromm Column: PLgel 10μ MIXED-B, inner diameter 7.5 mm x 300 mm (3 columns), manufactured by Agilent Technologies Differential refractive index detector: Shodex RI-101, manufactured by Resonac Corporation Column calibration: EasiCal PS-1 polystyrene, manufactured by Agilent Technologies Eluent: tetrahydrofuran for HPLC, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Column temperature: 40°C Flow rate: 1.0 mL / min Mw / Mn was calculated from the obtained values. Mw and Mw / Mn are shown in Table 1.

[0065]

[0066] <Method for manufacturing surface protection composition> The obtained polymer (A), acid generator (B), and solvents such as acetone, ethyl acetate, propylene carbonate, and PGMEA, and water were mixed in the formulations shown in Table 2 using a mix rotor until homogeneous, thereby obtaining a surface protection composition for each example.

[0067] <Evaluation of cleaning properties> The surface protection compositions shown in Table 2 were applied to a substrate of glass (water slide glass, manufactured by Matsunami Glass Industrial Co., Ltd., S7213) or a silicon wafer (manufactured by Seiren KST Co., Ltd., product name: φ6" silicon wafer) using a non-wire bar coater OSP-80-L60 (film thickness 80 μm / wet), and dried in an oven at 100°C for 5 minutes to obtain a film coated on the substrate. The thickness of the film after drying was within the range of 10±5 μm. The obtained film was irradiated with light for each example under the following conditions.

[0068] <Light Irradiation Conditions> (Examples 1 to 3, 5, 7, 9, 10, 13 to 18 and Comparative Example 1) The substrate with the film was placed on a SUS table, and the illuminance was 7705 mW / cm ２ , irradiation time 30 seconds, cumulative light amount 230 J / cm２ The film-side surface of the substrate was irradiated with ultraviolet light having a wavelength of 365 nm using an LED light source (manufactured by Pi Photonics, product name: Hololite Kaku) under the conditions of 100°C to 120°C. The temperature of the film surface on the SUS stand during the light irradiation was measured using a radiation thermometer and found to be about 30°C.

[0069] (Examples 4, 8, 11 and 12) The obtained substrate with the film was placed on a SUS table, and the illuminance was 20 mW / cm ２ , irradiation time 120 seconds, cumulative light amount 2400 mJ / cm ２ The film side surface of the substrate was irradiated with light using a high-pressure mercury lamp (manufactured by Technovision Co., Ltd., product name: UVC-408) under the conditions of

[0070] (Example 6) The obtained substrate with the film was placed on a SUS table, and the illuminance was 20 mW / cm ２ , irradiation time 70 seconds, cumulative light amount 1400 mJ / cm ２ The film side surface of the substrate was irradiated with light using a high-pressure mercury lamp (manufactured by Technovision Co., Ltd., product name: UVC-408) under the conditions of

[0071] (Comparative Example 2) The obtained substrate with the film was placed on a SUS table, and the illuminance was 20 mW / cm ２ , irradiation time 100 seconds, cumulative light amount 2000 mJ / cm ２ The film side surface of the substrate was irradiated with light using a high-pressure mercury lamp (manufactured by Technovision Co., Ltd., product name: UVC-408) under the conditions of

[0072] Next, the substrate and the film were immersed in water, and the time until the entire film was dissolved in water (dissolution time (minutes)) was measured. In addition, the cleaning ability was evaluated according to the following criteria. The results are shown in Table 2. (Criteria) A: The entire film was dissolved within 10 minutes. B: After 10 minutes, the film was completely peeled off from the substrate, or the film was partially dissolved. C: The film was neither dissolved nor peeled off within 10 minutes.

[0073] <Evaluation of Water Resistance> The surface protection compositions shown in Table 2 were applied to a substrate of glass (water slide glass, manufactured by Matsunami Glass Industrial Co., Ltd., S7213) or a silicon wafer (manufactured by Seiren KST Co., Ltd., product name: φ6" silicon wafer) using a non-wire bar coater OSP-80-L60 (film thickness 80 μm / wet), and dried in an oven at 100°C for 5 minutes to obtain a film coated on the substrate. The thickness of the film after drying was within the range of 10±5 μm. Next, the substrate and the film were immersed in water for 10 minutes, and then removed from the water. The state of the substrate and the film was observed and the water resistance was evaluated according to the following (criteria). A was considered to be acceptable. The results are shown in Table 2. (Criteria) A: The film did not dissolve and was adhered to the substrate. B: The film peeled off from the substrate. C: The film became cloudy or dissolved.

[0074]

[0075] This application claims priority based on Japanese Patent Application No. 2024-055765, filed March 29, 2024, the disclosure of which is incorporated herein in its entirety by reference.

Claims

1. A surface protection composition comprising: a polymer (A) containing a structural unit (a) derived from a (meth)acrylate (a) having an acid-decomposable group; and an acid generator (B) containing at least one selected from a photoacid generator and a thermal acid generator, wherein a product derived from the polymer (A) after acid decomposition of the acid-decomposable group has a hydrophilic group.

2. The surface protecting composition according to claim 1, wherein a film made of the surface protecting composition does not peel off from the substrate, does not become cloudy, or does not dissolve when the following <Method 1> is carried out: <Method 1> A film made of the surface protecting composition and having a thickness of 10±5 μm is formed on a substrate, and then the substrate and the film are immersed in water for 10 minutes, and then the substrate and the film are removed from the water.

3. The surface protecting composition according to claim 1 or 2, wherein the (meth)acrylate (a) comprises a methacrylate.

4. The surface protecting composition according to any one of claims 1 to 3, wherein the functional group protected by the acid-decomposable group includes a carboxyl group.

5. The surface protecting composition according to any one of claims 1 to 4, wherein the acid-decomposable group includes a group containing an ether bond.

6. The surface protecting composition according to claim 5, wherein the group containing an ether bond includes an alkyl group having 1 to 8 carbon atoms.

7. The surface protecting composition according to claim 6, wherein the alkyl group is linear.

8. A surface protecting composition according to any one of claims 1 to 7, wherein the polymer (A) further contains structural units (b) derived from one or more monomers (b) selected from the group consisting of (meth)acrylic acid, (meth)acrylamide, and (meth)acrylates containing an ether bond.

9. The surface protecting composition according to any one of claims 1 to 8, wherein the weight average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography in terms of polystyrene is 5,000 or more and 10,000,000 or less.

10. The surface protecting composition according to any one of claims 1 to 9, wherein the acid generator (B) includes a photoacid generator.

11. The surface protecting composition according to claim 10, wherein the photoacid generator comprises one or two selected from the group consisting of a sulfonium salt-type photoacid generator, an iodonium salt-type photoacid generator, and a non-ionic photoacid generator.

12. A surface protecting composition according to any one of claims 1 to 11, wherein the content of the acid generator (B) is 1.0 part by mass or more and 50 parts by mass or less per 100 parts by mass of the polymer (A).

13. A surface protective film comprising the surface protective composition according to any one of claims 1 to 12.

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