polymer and curable resin composition containing the same

Abstract

The objective is to provide a polymer that, when added to a resin composition, imparts high leveling properties equivalent to those of a fluorine-based surface modifier. Furthermore, the objective is to provide a polymer that imparts water repellency to a resin composition and maintains high durability, even after washing. [Solution] A polymer comprising monomer (A) represented by formula (1) and monomer (B) represented by formula (6) as constituent monomers, wherein monomer (A) accounts for 10 to 90% by mass and monomer (B) accounts for 10 to 90% by mass of the total mass of monomer (A) and monomer (B), and the weight-average molecular weight is 3,000 to 3,000,000.

Description

[Technical Field]

[0001] The present invention relates to polymers and curable resin compositions containing the same. [Background technology]

[0002] Copolymers containing (meth)acrylic monomers are known as resins with excellent weather resistance, transparency, and processability, and are used in various fields such as paints and adhesives. One of these applications is as a surface modifier. Surface modifiers are added when applying compositions such as printing inks, paints, and coatings to smooth the surface of the coating film, or in resist compositions to improve the leveling properties of the coating film and form high-precision patterns.

[0003] As a surface modifier, for example, Patent Document 1 discloses an acrylic copolymer having a perfluoroalkyl group as a highly oriented surface modifier. However, in recent years, surface modifiers using fluorine raw materials have raised concerns about environmental impact and are subject to legal regulations, leading to a demand for non-fluorine-based surface modifiers. Furthermore, in the field of photoresists, the miniaturization and fineness of electronic components have made it essential to form finer patterns with higher precision than ever before. Therefore, in addition to basic properties such as good leveling properties, the materials that make up the photoresist must be able to avoid the inclusion of foreign substances such as moisture and dirt. It is known that if moisture or dirt adheres to the surface of the photoresist, it can cause shape defects during etching. Therefore, a method is known to prevent the adhesion of moisture and dirt by imparting water repellency to the surface of the coating film. For example, prior art 2 describes a photosensitive resin composition using a compound having a siloxy group. The cured film obtained from this composition has high flatness and water repellency. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-84012 [Patent Document 2] International Publication No. 2008 / 090827 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Resist materials are exposed to pure water or chemicals for a certain period of time during the washing and developing processes. When using non-fluorine-based surface modifiers, the water repellency may decrease during these processes, sometimes leading to defects such as shape defects in subsequent processes. Therefore, there is a need for non-fluorine-based materials that maintain high water repellency even after washing and developing processes with pure water or chemicals. The problem that this invention aims to solve is to provide a polymer that, when added to a resin composition, imparts high leveling properties equivalent to those of a fluorine-based surface modifier. Furthermore, it aims to provide a polymer that imparts water repellency to a resin composition and maintains high durability, even after washing. [Means for solving the problem]

[0006] As a result of repeated studies to solve the above problems, the present inventors have found that the above problems can be solved by adding a polymer consisting of a (meth)acrylic monomer having a hydroxyurethane structure and a hydrophilic (meth)acrylic monomer to a resin composition, and have completed the present invention. That is, the present invention relates to the following [1] to [2]. In other words, the present invention is as follows [1] to [2].

[0007] [1] A polymer comprising monomer (A) represented by the following formula (1) and monomer (B) represented by the following formula (6) as constituent monomers, wherein monomer (A) accounts for 10 to 90% by mass and monomer (B) accounts for 10 to 90% by mass of the total mass of monomer (A) and monomer (B), and the weight-average molecular weight is 3,000 to 3,000,000. [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, and R 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R 3 represents an aliphatic hydrocarbon group having 2 to 30 carbon atoms, and X is any structure selected from the group consisting of the hydroxyurethane structures of the following formulas (2), (3), (4) and (5).) [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] (In formula (6), R 4 represents a hydrogen atom or a methyl group, and R 5 represents a hydrogen atom or a methyl group. AO represents an oxyalkylene group having 2 to 4 carbon atoms, n represents the average number of added moles of the oxyalkylene group, and is a number from 1 to 100.) [2] A curable resin composition containing 0.01 to 20 parts by mass of the polymer according to claim 1 with respect to 100 parts by mass of the curable resin. [Advantages of the Invention]

[0008] According to the present invention, by adding it to a resin composition, a polymer capable of imparting a high leveling property equivalent to that of a fluorine-based surface conditioner can be provided. Further, according to the present invention, a polymer capable of imparting water repellency to a resin composition and having high durability against moisture can be provided. [Modes for Carrying Out the Invention]

[0009] In this specification, a numerical range defined using the symbol "~" shall include the numerical values at both ends (the upper limit and the lower limit) of "~". For example, "2~4" represents 2 or more and 4 or less. Also, in the present invention, "(meth)acryl" is a general term encompassing acrylic and methacrylic, and "(meth)acrylate" is a general term encompassing acrylate and methacrylate. Hereinafter, embodiments of the present invention will be described.

[0010] <Polymer> The polymer of the present invention contains a monomer (A) represented by the following formula (1) and a monomer (B) represented by the following formula (6) as constituent monomers. The content of each monomer is such that, with respect to a total of 100% by mass of monomer (A) and monomer (B), monomer (A) is 10 to 90% by mass and monomer (B) is 10 to 90% by mass. Further, the weight average molecular weight of the polymer is 3,000 to 3,000,000.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0011] The polymer of the present invention contains monomer (A) and monomer (B) as constituent monomers as described above. That is, the polymer of the present invention is a copolymer obtained by copolymerizing monomer components that contain at least monomer (A) and monomer (B). When the total content of all monomers contained in the polymer is 100% by mass, the total content of monomer (A) and monomer (B) is 80 to 100% by mass, but 100% by mass is more preferable. Monomer (A), which is a constituent monomer of the polymer of the present invention, may be used alone or in combination of two or more types. Similarly, monomer (B), which is a constituent monomer of the polymer of the present invention, may be used alone or in combination of two or more types. The monomers (A), (B), and polymers will be described below in order.

[0012] <Monomer (A)> In the present invention, monomer (A) is represented by the following formula (1). [ka] (In formula (1), R 1 R represents a hydrogen atom or a methyl group. 2 R represents a single bond or an alkylene group having 1 to 4 carbon atoms. 3 represents an aliphatic hydrocarbon group having 2 to 30 carbon atoms, and X is one of the structures selected from the group consisting of hydroxyurethane structures of formulas (2), (3), (4), and (5) below.

[0013] In formula (1), R 1 R is either a hydrogen atom or a methyl group, and a hydrogen atom is preferred from the viewpoint of reactivity. 2R is a single bond or an alkylene group having 1 to 4 carbon atoms. Examples of alkylene groups having 1 to 4 carbon atoms include methylene (-CH2-), ethylene (-CH2-CH2-), propylene (-CH2-CH2-CH2-), and butylene (-CH2-CH2-CH2-CH2-), with single bonds being preferred. 2 If it is a single bond, it means that O (oxygen atom) and X are directly bonded in equation (1). R 3 R is an aliphatic hydrocarbon group having 2 to 30 carbon atoms. Examples of such aliphatic hydrocarbon groups include alkyl groups having 2 to 30 carbon atoms, such as ethyl group, butyl group, hexyl group, octyl group, ethylhexyl group, nonyl group, decyl group, lauryl group, stearyl group, and behenyl group. From the viewpoint of improving the leveling properties and compatibility with the resin of the polymer-containing resin composition, 3 A C10-C26 alkyl group is preferred, a C12-C22 alkyl group is more preferred, and a C16-C18 alkyl group is even more preferred. Also, R 3 It can be either a straight chain or branched, but a straight chain is preferred.

[0014] In formula (1), X is one structure selected from the group consisting of the hydroxyurethane structures of formulas (2), (3), (4), and (5) below. From the viewpoint of improving leveling properties and water repellency, the structure of formula (2) or formula (3) is preferred for X, and formula (2) is more preferred. Note that the leftmost carbon atom shown in formulas (2) to (5) above is R in formula (1). 2 It combines with the rightmost nitrogen atom shown in equations (2) to (5), and the R in equation (1) 3 It combines with it.

[0015] [ka] [ka] [ka] [ka]

[0016] The method for producing monomer (A) represented by formula (1) is not particularly limited and can be produced by known methods, but for example, it can be obtained by an addition reaction between a compound having both a (meth)acryloyl group and a cyclic carbonate group and an amine compound having an alkyl group with 2 to 30 carbon atoms. Monomer (A) represented by formula (1) may be used alone or in combination of two or more types. When the total content of monomer (A) and monomer (B) in the polymer is 100% by mass, the content of monomer (A) is 10 to 90% by mass. If the content of monomer (A) exceeds 90% by mass, although water repellency is excellent, compatibility with solvents and curable resins in which it dissolves during compounding decreases, and leveling properties may deteriorate. On the other hand, if the content of monomer (A) is less than 10% by mass, although compatibility with solvents and curable resins in which it dissolves during compounding is excellent, orientation decreases, and leveling properties, water repellency, and water resistance may deteriorate. For this reason, the content of monomer (A) is set to 10 to 90% by mass, but the lower limit of the monomer (A) content is preferably 30% by mass, and more preferably 45% by mass. The upper limit of the monomer (A) content is preferably 70% by mass, and more preferably 55% by mass. The amount of monomer (A) contained in the polymer corresponds to the ratio of the mass of monomer (A) to the total mass of monomer (A) and monomer (B) used in polymerizing the polymer. The same applies to the amount of monomer (B) described later.

[0017] <Monomer (B)> The monomer (B) of the present invention is represented by the following formula (6). [ka] (In formula (6), R 4 R represents a hydrogen atom or a methyl group. 5 represents a hydrogen atom or a methyl group. AO represents an oxyalkylene group with 2 to 4 carbon atoms, and n represents the average number of moles of oxyalkylene groups added, a number between 1 and 100.

[0018] In formula (2), R 4 , R 5 Each of these can be an independent hydrogen atom or a methyl group, and there are no particular limitations on their combinations. In formula (2), AO may be selected from oxyalkylene groups having 2 to 4 carbon atoms, and is preferably one or more selected from such oxyalkylene groups. Specifically, AO is preferably one or more selected from the group consisting of oxyethylene groups, oxypropylene groups, and oxybutylene groups. These oxyalkylene groups are obtained by addition polymerization of ethylene oxide, propylene oxide, butylene oxide, and tetramethylene oxide. The oxypropylene and oxybutylene groups may be linear or branched. AO is preferably one, two, or three oxyalkylene groups having 2 or 3 carbon atoms, and more preferably an oxyethylene group. When two or more types of AO are present, the addition form of -(AO)n- may be block or random. That is, it may be block, random, or both block and random. In formula (2), n represents the average number of moles of oxyalkylene groups added and is a number from 1 to 100. The lower limit of n is preferably 2, more preferably 4, even more preferably 6, and particularly preferably 7. The upper limit of n is preferably 50, more preferably 30, even more preferably 20, and particularly preferably 10. In the present invention, only one type of monomer (B) represented by formula (2) may be used, or two or more types may be used in combination. When the total content of monomer (A) and monomer (B) in the polymer is 100% by mass, the content of monomer (B) is 10 to 90% by mass, but the lower limit of the monomer (B) content is preferably 30% by mass, and more preferably 45% by mass. The upper limit of the monomer (B) content is preferably 70% by mass, and more preferably 55% by mass. By setting the content within this range, a polymer can be obtained that imparts high leveling properties, water repellency, and high durability against moisture to the resin composition. Monomer (B) can be synthesized according to standard methods, but commercially available monomers can also be used.

[0019] <Other monomer components> The polymer of the present invention may contain other monomer components (hereinafter referred to as monomer (C)) different from monomer (A) and monomer (B) as constituent monomers. Preferred monomers (C) include, for example, those having radically polymerizable functional groups such as acryloyl groups, methacryloyl groups, and vinyl groups as reactive functional groups. Examples include (meth)acrylic acid esters of monoalcohols, and N-cyclohexylmaleimide and N-vinylpyrrolidone, which possess both vinyl and alicyclic hydrocarbon groups. Low-viscosity acrylates or methacrylates, generally known as reactive diluents, may also be used as monomer (C). The monomer (C) content is preferably 0 to 20% by mass, when the total monomer content in the polymer is taken as 100% by mass. The upper limit of the monomer (C) content is more preferably 3% by mass. Including monomer (C) within this range may improve solubility in solvents and curable resins used when preparing the curable resin composition, and improve leveling properties.

[0020] <Molecular weight of polymer> The weight-average molecular weight of the polymer of the present invention may be between 3,000 and 3,000,000, but the lower limit of the weight-average molecular weight is preferably 10,000, and more preferably 15,000. The upper limit of the weight-average molecular weight is preferably 300,000, and more preferably 150,000. If the weight-average molecular weight is lower than 3,000, there is a tendency for insufficient leveling and water resistance, and if the weight-average molecular weight is higher than 3,000,000, there is a tendency for leveling to decrease due to poor compatibility. The weight-average molecular weight of the polymer can be determined in polystyrene terms using gel permeation chromatography (GPC).

[0021] <Polymerization method> Next, a method for producing the polymer of the present invention will be described. Polymers can be obtained, for example, by radical polymerization of a mixture of the aforementioned monomers in the presence of a polymerization initiator. Polymerization can be carried out by known methods. Examples include solution polymerization, suspension polymerization, and emulsion polymerization, but solution polymerization is preferred because it is easy to adjust the weight-average molecular weight of the polymer within the above range. Examples of polymerization initiators include organic peroxides such as t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, and dicumyl peroxide, as well as azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, and 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine] dihydrochloride. These polymerization initiators may be used individually or in combination of two or more. The amount of polymerization initiator used can be appropriately determined depending on the combination of monomers used and the reaction conditions. When polymerizing the aforementioned monomers in the presence of a polymerization initiator, the entire amount may be added at once, a portion may be added at once and the remainder added dropwise, or the entire amount may be added dropwise. Due to the ease of controlling the exothermic reaction, it is preferable to add a portion at once and the remainder added dropwise, or to add the entire amount dropwise. Furthermore, it is preferable to add the polymerization initiator after the monomer has been added dropwise, as this can reduce the amount of residual monomer.

[0022] As polymerization solvents used in solution polymerization, any solvent that dissolves the monomer and polymerization initiator can be used. Specifically, examples include toluene, xylene, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and methyl ethyl ketone. The concentration of monomer (total amount) per 100 parts by mass of polymerization solvent is preferably 20 to 80 parts by mass. The lower limit of the monomer (total amount) concentration is more preferably 40 parts by mass. If the concentration of the monomer mixture is too low, monomers are likely to remain, which may reduce the molecular weight of the resulting copolymer. If the monomer concentration is too high, it may become difficult to control the exothermic reaction.

[0023] The polymerization temperature can be appropriately set depending on the type of monomer and the type of polymerization solvent, for example, between 50°C and 120°C. The polymerization time can also be appropriately set depending on the type of polymerization initiator and the polymerization temperature. For example, when t-butyl peroxyneodecanoate is used as the polymerization initiator, a polymerization time of approximately 3 to 6 hours is suitable when polymerization is carried out at a polymerization temperature of 75°C. By carrying out the polymerization reaction described above, the polymer of the present invention can be obtained. The obtained polymer may be used as is, or the reaction solution after the polymerization reaction may be filtered or purified to isolate it.

[0024] <Surface modifier> The surface modifier of the present invention may contain the aforementioned polymer. Therefore, it may consist only of the aforementioned polymer, or it may contain other surface modifiers and / or other components that have components other than the aforementioned polymer as active ingredients. Examples of other surface modifiers include silicone resins, acrylic silicone resins, acrylic resins, etc. Examples of other components include non-reactive resins (plasticizers, stress reducers, etc.), antioxidants, UV absorbers, fillers, etc. Only one of the other surface modifiers and other components may be used, or two or more may be used in combination. The content of other surface modifiers and other components, if included, can be appropriately determined depending on the application. Since the aforementioned polymer does not contain fluorine atoms, by ensuring that other surface modifiers and other components do not contain fluorine raw materials, it is possible to provide a surface modifier that does not contain fluorine raw materials and has a low environmental impact. Furthermore, although the surface modifier containing the aforementioned polymer does not contain fluorine raw materials, it can impart leveling properties to resin compositions such as the curable resin compositions described later to the same extent as conventional fluorine-based surface modifiers, and is suitable as a resin leveling agent. Furthermore, the aforementioned polymer has high water repellency and water resistance, and suppresses the adhesion of moisture and dirt to the coating surface, making it suitable as a leveling agent used in the resist field.

[0025] <Curable resin composition> The curable resin composition of the present invention contains the aforementioned polymer and curable resin. In the curable resin composition, the content of the aforementioned polymer is preferably 0.01 to 20 parts by mass per 100 parts by mass of curable resin, the lower limit of the polymer content is preferably 0.1 parts by mass, more preferably 0.2 parts by mass, and the upper limit of the polymer content is preferably 15 parts by mass, more preferably 10 parts by mass.

[0026] The curable resin usable in the curable resin composition of the present invention is not particularly limited, but it is preferably a photocurable resin and / or a thermosetting resin. In this specification, curable compounds that do not have the properties of a resin, such as low molecular weight monofunctional acrylic monomers, are also described as curable resins. Examples of thermosetting resins include epoxy resins, phenolic resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins. While not limited to these, known thermosetting resins can be used, but epoxy resins and phenolic resins are preferred from the viewpoint of compatibility. Photocurable resins include, for example, resins having vinyl groups, vinyl ether groups, allyl groups, maleimide groups, (meth)acryloyl groups, etc. Examples include poly(meth)acrylic acid resins, polyvinyl ether resins, urethane acrylate resins, epoxy acrylate resins, polyester acrylate resins, alicyclic epoxy resins, glycidyl epoxy resins, etc.

[0027] The curable resin composition of the present invention may contain a polymerization initiator depending on the type of curable resin described above. The polymerization initiator is a compound that serves as the starting point for polymerization reactions of the curable resin, and known thermal polymerization initiators and photopolymerization initiators can be used. The polymerization initiator in the present invention can be used alone or in combination of two or more types.

[0028] As a thermal polymerization initiator, polymerization initiators used in the production of the polymer of the present invention, polyisocyanates, etc., can be used. Examples of polyisocyanates include, but are not limited to, Duranate SBN-70D manufactured by Asahi Kasei Corporation. When using a photopolymerization initiator, there are no particular limitations on the wavelength of the light used for irradiation, but a photopolymerization initiator suitable for the wavelength can be selected and used. Examples of photopolymerization initiators include aromatic ketones such as benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, 4,4'-bis(dimethylamino)benzophenone (Michler ketone), 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone; quinones such as alkylanthraquinone and phenanthrenequinone; benzoin compounds such as benzoin and alkylbenzoin; benzoin ether compounds such as benzoin alkyl ether and benzoin phenyl ether; benzyl derivatives such as benzyldimethylketal; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer; and 2-(o-chlorophenyl)-4,5-di(m-methoxyf 2,4,5-triarylimidazole dimers such as phenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, N-phenylglycine, N-phenylglycine derivatives, Acridine derivatives such as 9-phenylacridine, oxime esters such as 1,2-octanedione and 1-[4-(phenylthio)-,2-(O-benzoyloxime)], coumarin compounds such as 7-diethylamino-4-methylcoumarin, thioxanthone compounds such as 2,4-diethylthioxanthone, and acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide can be used.

[0029] The content of the polymerization initiator in the curable resin composition of the present invention is preferably 0.01% to 50% by mass with respect to the total solid content of the curable resin composition, with the lower limit of the polymerization initiator content being preferably 0.1% by mass. The upper limit of the polymerization initiator content is preferably 25% by mass, and more preferably 15% by mass.

[0030] <Solvents, other ingredients> The curable resin composition of the present invention may contain solvents and other components, as long as they do not impair the effects of the present invention. Known solvents can be used. Examples include methyl alcohol, ethyl alcohol, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, N,N-dimethylformamide, tetrahydrofuran, benzene, toluene, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate. One solvent may be used alone, or two or more may be used in combination. When a solvent is used, the solvent content is preferably 40 to 400 parts by mass per 100 parts by mass of curable resin, with a lower limit of 150 parts by mass being more preferable. The upper limit of the solvent content is more preferably 300 parts by mass. Other components include, for example, heat-resistant enhancers, developing aids, inorganic fine particles, coupling agents, fillers, curing agents, plasticizers, polymerization inhibitors, antioxidants, defoamers, viscosity modifiers, and pigments. These other components may be used individually or in combination of two or more. Their content is 0 to 20% by weight of the total composition, with a preferred upper limit of 15% by weight and more preferably 10% by weight.

[0031] The curable resin composition of the present invention is prepared by appropriately mixing the polymer of the present invention and the curable resin, as well as polymerization initiators, solvents, and other components as needed. The manufacturing method is not particularly limited, but it can be prepared by mixing the above components using various mixers and dispersers. The mixing method is not particularly limited; all components may be mixed simultaneously, or each component may be mixed sequentially. The mixing order and working conditions are not particularly limited and can be adjusted by known methods. Because the curable resin composition contains the aforementioned polymer, it has good leveling properties, water repellency, and high durability against moisture, which can suppress defects during etching and developing processes in the resist field when the curable resin composition is applied.

[0032] <Cured film> A cured film can be obtained by curing the aforementioned curable resin composition. The cured film can be obtained by various known methods. For example, a cured film can be obtained by applying the curable resin composition to the surface of a substrate to form a coating film and then curing the curable resin. The method of applying the curable resin composition is not particularly limited, and examples include using a coating device such as a spin coater, spray coater, slit coater, or inkjet. A cured film can be obtained by applying the curable resin composition onto a substrate and then appropriately selecting and going through processes such as drying, pre-baking, photocuring, developing, washing, and post-baking depending on the type of curable resin. The curing conditions vary depending on the type and mixing ratio of each component, but as heating conditions, for example, a range of 70 to 150°C for 1 to 30 minutes is preferred. In photocuring, exposure is performed using ultraviolet light such as i-rays, h-rays, and g-rays, or an ArF laser or KrF laser as the exposure light source. Exposure may also be performed through a mask having a predetermined pattern. The cured film formed using the aforementioned curable resin composition with good leveling properties exhibits low and good surface roughness (Pa) on the cured film surface, similar to cases containing conventional fluorine-based surface modifiers, as well as high water repellency and water resistance. These properties can be evaluated by the evaluation method described in the Examples section below. [Examples]

[0033] The embodiments of the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following embodiments.

[0034] (Synthesis of monomer (A)) Monomers A-1 to A-6 used in the examples and monomer A'-1 used in the comparative example are each R in formula (1). 1 ~R 3 X is a compound having the structure shown in Table 1. Note that "-" in Table 1 indicates a single bond.

[0035] <Synthesis of Monomer A-1> In a reaction apparatus equipped with a stirrer and thermometer, 60 parts by mass of stearylamine, 500 parts by mass of heptane, and 0.05 parts by mass of methoxyphenol were placed and stirred at room temperature for 1 hour to dissolve the stearylamine. 30 parts by mass of (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate (manufactured by NOF Corporation, trade name: Bremmer DO-MA) were added dropwise to the reaction apparatus over 10 minutes and the reaction was carried out at room temperature for 16 hours. 1 The reaction was confirmed to have ended when the peak for the starting material (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate disappeared by 1H NMR spectroscopy. The reaction mixture was placed in a pressure filter and the solid was recovered by pressure filtration with nitrogen gas. Monomer A-1 was obtained by vacuum drying of the recovered solid.

[0036] <Synthesis of Monomer A-2> It was synthesized in the same manner as monomer A-1, except that (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate was replaced with (2-oxo-1,3-dioxolan-4-yl)methyl acrylate.

[0037] <Synthesis of Monomer A-3> It was synthesized in the same manner as monomer A-1, except that stearylamine was replaced with behenylamine.

[0038] <Synthesis of Monomer A-4> It was synthesized in the same manner as monomer A-1, except that stearylamine was replaced with octylamine.

[0039] <Synthesis of Monomer A-5> It was synthesized in the same manner as monomer A-1, except that (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate was replaced with (2-oxo-1,3-dioxolan-4-yl)butyl methacrylate.

[0040] <Synthesis of Monomer A-6> It was synthesized in the same manner as monomer A-1, except that (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate was replaced with (2-oxohexahydrobenzo-1,3-dioxol-5-yl)methyl methacrylate.

[0041] <Synthesis of monomer A'-1> It was synthesized by dehydration esterification of methacrylic acid and stearyl alcohol.

[0042] [Table 1]

[0043] The monomers (B) used in the examples are each R in formula (6). 4 ~R 5 AO and n are compounds (monomers B-1 to B-7) having the structures shown in Table 2.

[0044] [Table 2]

[0045] <Synthesis of polymers> (Synthesis of Polymer 1) 139.0 g of propylene glycol monomethyl ether was placed in a 1 L separable flask equipped with a stirrer, thermometer, condenser, dropping funnel, and nitrogen inlet tube, and the flask was purged with nitrogen to create a nitrogen atmosphere. The temperature inside the reaction vessel was raised to 75°C, and 15.0 g of monomer A-1, 85.0 g of PME-400 (product name: Bremmer PME-400, manufactured by NOF Corporation), and a solution of 10.0 g of propylene glycol monomethyl ether in which 9.0 g of t-butyl peroxyneododecanate was dissolved were added. After reacting at 75°C for 30 minutes, an additional solution of 1.0 g of propylene glycol monomethyl ether in which 0.2 g of t-butyl peroxyneododecanate was added. The reaction was then continued at 75°C for 3 hours. Polymer 1 was obtained by drying the resulting polymerization solution under reduced pressure at 120°C.

[0046] (Synthesis of polymers 2-16 and 19-21) The synthesis was carried out in the same manner as the synthesis of polymer 1, except that the types and amounts of monomers (A) and monomer (B) were as shown in Table 3.

[0047] (Synthesis of polymer 17) Polymer 1 was synthesized in the same manner as polymer 1, except that the amount of monomer (A) and monomer (B) used was changed to 50.0g, and the amount of t-butylperoxyneododecanate was changed from 9.0g to 30g.

[0048] (Synthesis of Polymer 18) The polymer was synthesized in the same manner as polymer 1, except that the amount of monomer (A) and monomer (B) used was changed to 50.0g, and the amount of t-butylperoxyneododecanate was changed from 9.0g to 1.5g.

[0049] <Evaluation of polymers> [Measurement of weight-average molecular weight (Mw)] The weight-average molecular weight (Mw) of polymers 1 to 21 was determined using gel permeation chromatography (GPC) under the following conditions. Equipment: HLC-8220, manufactured by Tosoh Corporation. Column: manufactured by Resonac Corporation, Shodex LF-804 Standard material: Polystyrene Eluent: THF (tetrahydrofuran) Flow rate: 1.0mL / min Column temperature: 40℃ Detector: RI (Differential Refractive Index Detector)

[0050] [Table 3]

[0051] <Preparation of thermosetting resin composition> A thermosetting resin composition was prepared by mixing 70 parts by mass of phenolic resin (manufactured by Gun-ei Chemical Industry Co., Ltd., PL-5208, solids content 59% by mass, solvent: diethylene glycol diethyl ether) and 30 parts by mass of propylene glycol monomethyl ether.

[0052] <Example 1> Polymer 1 was blended into a thermosetting resin composition at a ratio of 0.5 parts by mass per 100 parts by mass of the curable resin, and the leveling properties, water repellency, and durability were evaluated. The results are shown in Table 4.

[0053] <Examples 2-20> Except for the type and amount of polymer used, as shown in Table 4, leveling properties, water repellency, and durability were evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0054] <Comparative Example 1> Except for replacing polymer 1 with polymer 19, the leveling properties, water repellency, and durability were evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0055] <Comparative Example 2> Except for replacing polymer 1 with polymer 20, the leveling properties, water repellency, and durability were evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0056] <Comparative Example 3> Except for replacing polymer 1 with polymer 21, leveling properties, water repellency, and durability were evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0057] <Comparative Example 4> Except for replacing polymer 1 with a silicone-based surface modifier (Disparon LS-009, manufactured by Kusumoto Chemical Co., Ltd.), leveling properties, water repellency, and durability were evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0058] <Comparative Example 5> Except for replacing polymer 1 with an acrylic surface modifier (Disparon LF-1984, manufactured by Kusumoto Chemical Co., Ltd.), leveling properties, water repellency, and durability were evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0059] <Comparative Example 6> Except for replacing polymer 1 with an acrylic silicone-based surface modifier (Disparon LHP-810, manufactured by Kusumoto Chemical Co., Ltd.), leveling properties, water repellency, and durability were evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0060] <Preparation of hardened film> The prepared thermosetting resin composition was applied to a glass substrate using a non-wire bar coater (OSP-150, φ10 × 60 mm), pre-baked on a hot plate at 80°C for 5 minutes, and then dried on a hot plate at 150°C for 15 minutes to form a cured film consisting of a layer of thermosetting resin composition.

[0061] <Leveling properties> As an indicator of the leveling properties of the obtained cured film, the arithmetic mean roughness (Pa) was measured using a stylus-type surface roughness analyzer (BRUKER, DektakXT). Leveling properties were determined according to the following evaluation criteria. A smaller Pa value indicates higher leveling properties. ◎: Pa is less than 0.25 μm ○: Pa is between 0.25 μm and less than 0.40 μm △: Pa is between 0.40 μm and less than 0.60 μm ×: Pa is 0.60 μm or larger

[0062] <Water repellency> The water repellency of the obtained cured film was evaluated using a contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.). The measurement conditions were as follows: 1.5 μL of water was dropped, and the contact angle of the water was measured using the liquid drop method (θ / 2 method). The measurement data is the contact angle value 1 second after water drop, and the average value of n=3 was used. Water repellency was determined according to the evaluation criteria below. A larger contact angle indicates higher water repellency. ◎: Contact angle of 90° or more ○: Contact angle is 85° or more and less than 90° △: Contact angle is between 80° and less than 85° ×: Contact angle is less than 80°

[0063] <Water resistance> A glass substrate with a cured film was immersed in pure water at 50°C and subjected to ultrasonic treatment for 5 minutes. Afterward, the surface of the cured film was washed with isopropanol for 10 seconds. The water repellency after the washing treatment was evaluated from the contact angle obtained using the same procedure as the "water repellency" test method described above, and the water resistance was evaluated by calculating the rate of change of the contact angle using the following formula. Rate of change (%) = (Contact angle after cleaning / Initial contact angle) × 100 Note that the initial contact angle is the contact angle of the cured film before cleaning treatment, and is the contact angle measured in the "water repellency" test described above. Water resistance was determined using the following evaluation criteria. A rate of change closer to 100% indicates higher water resistance. ◎: Rate of change is 95% or higher ○: Rate of change between 90% and less than 95% △: Rate of change between 85% and less than 90% ×: Rate of change is less than 85%

[0064] [Table 4]

[0065] As shown in Table 4, Examples 1-20 were found to have an arithmetic mean roughness of less than 0.6 μm, demonstrating good leveling properties. Furthermore, they were found to have a water contact angle of 80° or more, indicating high water repellency, and also possess high durability, maintaining water repellency even after washing. In Comparative Example 1, the cohesive force of the long-chain alkyl group was weak and the leveling properties were low because monomer (A) did not have a hydroxyurethane structure. In Comparative Example 2, the content of monomer (A) was low and 95% of the polymer was monomer (B), resulting in low leveling properties and water repellency. In Comparative Example 3, the content of monomer (B) was low and 95% of the polymer was monomer (A), resulting in poor orientation and low leveling properties. In Comparative Example 4, because it had a siloxy group, hydrolysis progressed during washing, reducing water repellency and resulting in low durability. In Comparative Example 5, because it did not contain monomer (A) or monomer (B), it had low leveling properties and water repellency. In Comparative Example 6, because it did not contain monomer (A) or monomer (B) and had a siloxy group, water repellency also decreased after washing. As described above, by adding a polymer composed of predetermined monomers to a curable resin composition, it is possible to impart high leveling properties. Furthermore, this polymer can impart water repellency to the curable resin composition and provide high durability, maintaining water repellency even after washing. Therefore, it is clear that this polymer is suitable as a surface modifier and leveling agent used in resist applications.

Claims

1. A polymer comprising monomer (A) represented by the following formula (1) and monomer (B) represented by the following formula (6) as constituent monomers, wherein monomer (A) accounts for 10 to 90% by mass and monomer (B) accounts for 10 to 90% by mass of the total mass of monomer (A) and monomer (B), and the weight-average molecular weight is 3,000 to 3,000,000. 【Chemistry 1】 (In formula (1), R １ R represents a hydrogen atom or a methyl group. ２ R represents a single bond or an alkylene group having 1 to 4 carbon atoms. ３ (wherein X represents an aliphatic hydrocarbon group having 2 to 30 carbon atoms, and X is one of the structures selected from the group consisting of hydroxyurethane structures of formulas (2), (3), (4), and (5) below.) 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 (In formula (6), R ４ R represents a hydrogen atom or a methyl group. ５ represents a hydrogen atom or a methyl group. AO represents an oxyalkylene group with 2 to 4 carbon atoms, and n represents the average number of moles of oxyalkylene groups added, a number from 1 to 100.

2. A curable resin composition containing 0.01 to 20 parts by mass of the polymer described in claim 1 per 100 parts by mass of a curable resin.

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