Polymer, surface conditioning agent containing polymer, and curable resin composition

Abstract

To provide a polymer that enables provision of a surface conditioning agent in which insoluble matter does not precipitate in solvents used in resist applications and the like, metal elution is reduced, and leveling properties equivalent to those of a fluorine-based surface conditioning agent can be imparted without use of the fluorine-based surface conditioning agent.SOLUTION: A polymer contains, as constituent monomers, a monomer A represented by the following formula (1) and a (meth)acrylate monomer B having a polyoxyalkylene group with an average added mole number of 1-100, the polymer containing, on a mass basis, 0.001-100 ppm of metal relative to a total of 100 mass% of the monomers A and B, and having a weight average molecular weight of 3000-3000000. (In formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 1-4 carbon atoms, and R3CO- represents an acyl group having 2-30 carbon atoms, wherein R3 is an aliphatic hydrocarbon group.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer, and a surface conditioner and a curable resin composition containing the polymer. [Background technology]

[0002] Copolymers containing (meth)acrylic monomers as constituent monomers are used in fields such as molding materials, paints, and adhesives, and are known as resins characterized by excellent weather resistance, transparency, and processability. One example of their use is as a surface conditioner. Surface conditioners are incorporated to control the surface tension of compositions that form coating films, such as paints and resist compositions, and are called antifoaming agents, leveling agents, anti-foaming agents, etc., depending on the purpose. As such, surface conditioners are incorporated into various compositions depending on the purpose, and therefore it is essential that they have good solubility in each component of the composition used, particularly water and organic solvents, and exhibit the desired performance.

[0003] Acrylic copolymers containing fluorine raw materials (perfluoroalkyl groups) are mainly used as surface conditioners because they have high orientation. Patent Document 1 proposes a fluorine-based surfactant that has high solubility in water and various solvents and excellent leveling performance. However, because this surfactant uses fluorine raw materials, there are concerns about the environmental impact when used as a fluorine-based surface conditioner.

[0004] Patent Document 2 proposes non-fluorine-based surface conditioners such as (meth)acrylic resins having hydrocarbon groups, siloxy groups, or ether groups as alternatives to fluorine-based surface conditioners. However, compared to fluorine-based surface conditioners, these have poor orientation and a low ability to reduce dynamic surface tension, which means that the desired leveling performance cannot be achieved.

[0005] In the field of resists, where surface conditioners are used, the formation of fine-line resist patterns has become more essential than ever in recent years due to the miniaturization and miniaturization of electronic products. Therefore, resist materials are required to not only have basic properties such as the absence of precipitation of insoluble matter derived from organic compounds and the ability to impart good leveling properties, but also to minimize the inclusion of impurities such as metallic foreign matter and metal components. Resist processes are broadly divided into resist application, exposure, development, etching, and resist removal. During the development process, unexposed resist components are dissolved and removed using an aqueous alkali metal solution. However, since Zr and Ti are insoluble in water, they remain on the substrate and wiring, raising concerns about wiring defects and adverse effects on the subsequent etching process.

[0006] Thus, when used in the resist or semiconductor fields, surface conditioners are required not to precipitate insoluble matters in water or solvents contained in various compositions used in these fields. In addition, there has been a demand for surface conditioners that cause little elution of metal components during processing and can impart leveling properties equivalent to those of fluorine-based surface conditioners to various compositions without using fluorine-based surface conditioners. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-292658 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-105786 Summary of the Invention [Problem to be solved by the invention]

[0008] The problem to be solved by the present invention is to provide a polymer capable of providing a surface conditioner having the following properties (i) to (iii), particularly a polymer suitable for use as a leveling agent in resist and semiconductor applications: (i) no insoluble matter precipitates in the solvents contained in various compositions used in the resist and semiconductor fields; (ii) minimal metal elution during processes in which various compositions used in the resist and semiconductor fields are applied; and (iii) the polymer is capable of imparting leveling properties equivalent to those of fluorine-based surface conditioners to various compositions, particularly curable resin compositions, without the use of such agents. Another problem is to provide a surface conditioner having such properties, and further to provide a curable resin composition that is free from insoluble matter precipitation, has good leveling properties, and suppresses metal elution during the aforementioned processes. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have found that the above-mentioned problems can be solved by using a specific polymer containing a predetermined monomer as a constituent monomer, intentionally incorporating a metal into the polymer, and designing the content of the metal contained in the polymer to be within a specific range, thereby completing the present invention. The gist of the present invention is as follows.

[0010] [1] A polymer comprising, as constituent monomers, a monomer (A) represented by the following formula (1) and a monomer (B) represented by the following formula (2), containing a metal in an amount of 0.001 ppm to 100 ppm by mass relative to 100% by mass of the total of the monomers (A) and (B), and having a weight-average molecular weight of 3,000 to 3,000,000.

[0011] [ka]

[0012] (In formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 4 carbon atoms, and R 3CO- has 2 to 30 carbon atoms, and R 3 indicates an acyl group of an aliphatic hydrocarbon group.)

[0013] [ka]

[0014] (In formula (2), R 4 , R 5 each independently represents a hydrogen atom or a methyl group, AO is selected from oxyalkylene groups having 2 to 4 carbon atoms, and n represents the average number of moles of oxyalkylene groups added and is a number from 1 to 100.

[0015] [2] The polymer according to [1] above, wherein the metal is at least one selected from the group consisting of iron, titanium, and zirconium. [3] A surface conditioner containing the polymer according to [1] or [2] above. [4] A curable resin composition comprising the polymer according to [1] or [2] above and a curable resin, the composition containing 0.01 to 20 parts by mass of the polymer per 100 parts by mass of the curable resin. [Effects of the Invention]

[0016] The present invention provides a polymer that can provide a surface conditioner having the following properties (i) to (iii), and in particular, can provide a polymer that is suitable for a leveling agent used in resist and semiconductor applications: (i) no insoluble matter precipitates in the solvents contained in various compositions used in the resist and semiconductor fields, (ii) little metal elution occurs during the process in which various compositions used in the resist and semiconductor fields are applied, and (iii) the polymer can impart leveling properties equivalent to those of a fluorine-based surface conditioner to various compositions, particularly curable resin compositions, without using a fluorine-based surface conditioner. Moreover, according to the present invention, it is possible to provide a surface conditioner having such properties, and further to provide a curable resin composition that is free from precipitation of insoluble matter, has good leveling properties, and is suppressed from eluting metal components during the above-mentioned process. DETAILED DESCRIPTION OF THE INVENTION

[0017] In addition, in this specification, "(meth)acrylic" is a generic term that includes acrylic and methacrylic, and "(meth)acrylate" is a generic term that includes acrylate and methacrylate. Terms such as "(meth)acryloyl group" have the same meaning as "(meth)acrylate."

[0018] Hereinafter, an embodiment of the present invention will be described.

[0019] <Polymer> A polymer according to an embodiment of the present invention contains, as constituent monomers, a monomer (A) represented by the following formula (1) and a monomer (B) represented by the following formula (2), and also contains a metal. The content of the metal is 0.001 ppm to 100 ppm by mass relative to 100% by mass of the total of the monomers (A) and (B). The weight-average molecular weight of the polymer is 3,000 to 3,000,000.

[0020] [ka]

[0021] (In formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 4 carbon atoms, and R 3 CO- has 2 to 30 carbon atoms, and R 3 indicates an acyl group of an aliphatic hydrocarbon group.)

[0022] [ka]

[0023] (In formula (2), R 4 , R 5 each independently represents a hydrogen atom or a methyl group, AO is selected from oxyalkylene groups having 2 to 4 carbon atoms, and n represents the average number of moles of oxyalkylene groups added and is a number from 1 to 100.

[0024] The monomer (A), the monomer (B), the metal and the polymer will be explained below.

[0025] [Monomer (A)] The monomer (A) applicable in the embodiment of the present invention may be any monomer as long as it is represented by the above formula (1).

[0026] In formula (1), R 1 may be a hydrogen atom or a methyl group, but is preferably a hydrogen atom from the viewpoint of reactivity.

[0027] In formula (1), R 2 is an alkylene group having 1 to 4 carbon atoms. The alkylene group having 1 to 4 carbon atoms may be a linear alkylene group or a branched alkylene group, but is preferably a linear alkylene group. The number of carbon atoms may be 1 to 4, but is preferably 2. Examples of linear alkylene groups having 1 to 4 carbon atoms include a methylene group (-CH2-), an ethylene group (-CH2-CH2-), a propylene group (-CH2-CH2-CH2-), and a butylene group (-CH2-CH2-CH2-CH2-), and of these, an ethylene group (-CH2-CH2-) is preferred.

[0028] In formula (1), R 3 CO- is an acyl group with 2 to 30 carbon atoms, and R 3 is an aliphatic hydrocarbon group, but is preferably an alkyl group. Examples of alkyl groups constituting the acyl group having 2 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethylhexyl, nonyl, decyl, undecyl, lauryl (dodecyl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl (octadecyl), nonadecyl, eicosyl, heneicosyl, and behenyl groups. From the viewpoint of leveling properties in the resin, R 3 The number of carbon atoms in CO- is preferably 4 to 26, more preferably 12 to 22. 3Although R may be either linear or branched, linear chains are preferred. Furthermore, when compatibility in the resin is taken into consideration, R 3 The number of carbon atoms in CO- is most preferably 12 to 18.

[0029] Only one type of monomer (A) may be contained, or two or more types may be contained.

[0030] The content of monomer (A) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 45 to 55% by mass, where the total content of the constituent monomers, monomer (A) and monomer (B), is 100% by mass. When the content of monomer (A) exceeds 90% by mass, the leveling property is excellent, but the solubility in the solvent and curable resin used in preparing the curable resin composition tends to be low. On the other hand, when the content of monomer (A) is less than 10% by mass, the leveling property tends to be poor, although the solubility in the solvent and curable resin used in preparing the curable resin composition is excellent.

[0031] Monomer (A) can be produced, for example, by (1) subjecting (meth)acrylic acid and an alkanolamide to a dehydration esterification reaction in the presence of an acid catalyst, (2) subjecting a (meth)acrylic acid ester and an alkanolamide to a transesterification reaction in the presence of a transesterification catalyst, or (3) reacting acrylic acid chloride with an alkanolamide. The various conditions can be appropriately selected according to the standard method, depending on the type of catalyst used and the types of synthetic raw materials. However, from the viewpoints of suppressing impurities and storage stability, a metal complex catalyst is preferably used as the catalyst, and a transition metal complex catalyst is more preferred. Examples of metal complex catalysts include iron complexes, titanium complexes, and zirconium complexes. Examples of zirconium complexes include zirconium(IV) acetylacetonate, and examples of titanium complexes include titanium acetylacetonate. Examples of iron complexes include iron(III) acetylacetonate. From the viewpoints of suppressing self-polymerization during storage and reactivity during production, titanium and zirconium complexes are preferred, and zirconium complexes are more preferred. The alkanolamide used may be prepared according to a standard method.

[0032] [Monomer (B)] The monomer (B) applicable in the embodiment of the present invention may be any monomer as long as it is represented by the above formula (2).

[0033] In formula (2), R 4 , R 5 may be each independently a hydrogen atom or a methyl group, and there are no particular limitations on the combinations thereof.

[0034] In formula (2), AO may be any oxyalkylene group having 2 to 4 carbon atoms, and is preferably one or more oxyalkylene groups selected from the group consisting of oxyethylene groups, oxypropylene groups, and oxybutylene groups. The oxypropylene group and oxybutylene group 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 AOs are present, the addition form of -(AO)n- may be either block or random. That is, it may be block, random, or both block and random.

[0035] In formula (2), n represents the average number of moles of oxyalkylene groups added, and is a number from 1 to 100. n is preferably a number from 2 to 90, more preferably a number from 4 to 50, and even more preferably a number from 6 to 25.

[0036] Only one type of monomer (B) may be contained, or two or more types may be contained.

[0037] The content of monomer (B) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 45 to 55% by mass, when the total content of monomers (A) and (B) is 100% by mass. Within this range, a polymer can be obtained that has excellent solubility in various solvents and does not reduce leveling properties. When the content of monomer (B) exceeds 90% by mass, the compatibility with the solvent and curable resin used to prepare the curable resin composition is excellent, but the leveling properties tend to deteriorate. On the other hand, when the content of monomer (B) is less than 10% by mass, the compatibility with the solvent and curable resin used during blending tends to be poor, although the leveling properties are excellent.

[0038] The monomer (B) can be synthesized according to a conventional method, but commercially available products can also be used.

[0039] [Other monomer components] The polymer according to the embodiment of the present invention may contain a monomer component (hereinafter referred to as "monomer (C)") other than the monomers (A) and (B) as a constituent monomer. Monomer (C) preferably has a radically polymerizable functional group such as an acryloyl group, a methacryloyl group, or a vinyl group as a reactive functional group. Examples of the monomer (C) include common (meth)acrylic acid esters having an alkyl group with 1 to 10 carbon atoms, and N-cyclohexylmaleimide and N-vinylpyrrolidone having both a vinyl group and an alicyclic hydrocarbon.

[0040] The content of the monomer (C) is preferably 0 to 20 parts by mass when the total content of the monomers (A) to (C) constituting the polymer is 100 parts by mass. By including the monomer (C) in this range, the leveling property tends to be improved with respect to the solvent and curable resin used in preparing the curable resin composition.

[0041] [metal] In the embodiment of the present invention, the metal contained in the polymer is not particularly limited, and may be selected from those classified as metallic elements in the periodic table, such as alkali metals, alkaline earth metals, and transition metals. From the viewpoints of compatibility with the curable resin used in the curable resin composition described below and solubility in solvents contained in compositions used in the resist field (prevention of insoluble matter formation), the metal is preferably selected from transition metals, more preferably at least one selected from iron, titanium, and zirconium, even more preferably at least one selected from titanium and zirconium, and particularly preferably zirconium. The metal may be incorporated into the polymer by separate addition, or may be derived from a raw material used in synthesizing the polymer, such as a monomer component. For example, a metal derived from a metal complex catalyst used in synthesizing the monomer (A) may be used.

[0042] Only one type of metal may be contained, or two or more types of metals may be contained.

[0043] The metal content may be 0.001 ppm to 100 ppm by mass relative to 100% by mass of the total of the monomers (A) and (B), but is preferably 0.005 to 50 ppm by mass or less, and more preferably 0.01 to 1 ppm by mass or less. The metal content in the polymer is not particularly limited and can be measured by a known method, for example, it can be measured and calculated using an inductively coupled plasma mass spectrometer (ICP-MS).

[0044] [Polymer] The polymer according to the embodiment of the present invention may be composed of only one type selected from those containing monomers (A) and (B) as constituent monomers, containing a metal in a predetermined range, and having a predetermined weight-average molecular weight, or may be a mixture of polymers composed of two or more types.

[0045] The weight-average molecular weight of the polymer according to the embodiment of the present invention may be 3,000 to 3,000,000, preferably 10,000 to 150,000, and more preferably 15,000 to 50,000. If the weight-average molecular weight is lower than 3,000, the leveling property tends to be insufficient, and if the weight-average molecular weight is higher than 3,000,000, the compatibility tends to be poor. The weight-average molecular weight of the polymer can be determined in terms of polystyrene using gel permeation chromatography (GPC).

[0046] (Polymerization method) Next, a method for producing a polymer according to an embodiment of the present invention will be described. The polymer can be obtained, for example, by radical polymerization of a mixture of the above-mentioned various monomers in the presence of a polymerization initiator. The polymerization can be carried out by a known method. For example, solution polymerization, suspension polymerization, emulsion polymerization, etc. are mentioned, but solution polymerization is preferred in that the weight-average molecular weight of the polymer can be easily adjusted to fall within the above range.

[0047] Known polymerization initiators can be used, including, for example, 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, and 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 alone or in combination of two or more.

[0048] The amount of the polymerization initiator used can be appropriately determined depending on the combination of monomers used, reaction conditions, and the like.

[0049] When polymerizing each of the above-mentioned monomers in the presence of a polymerization initiator, for example, the entire amount may be charged at once, or a portion may be charged at once and the remainder may be added dropwise, or the entire amount may be added dropwise. From the viewpoint of ease of heat generation control, it is preferable to charge a portion at once and the remainder may be added dropwise, or to add the entire amount dropwise. Furthermore, it is preferable to add a polymerization initiator after the monomer dropwise addition, since this can reduce the amount of residual monomer.

[0050] The polymerization solvent used in solution polymerization can be one in which the monomer and the polymerization initiator are soluble. Specific examples of the polymerization solvent include toluene, xylene, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and methyl ethyl ketone.

[0051] The concentration of the monomers (total amount) relative to the polymerization solvent is preferably 20 to 80% by mass, particularly preferably 40 to 80% by mass. If the monomer concentration is too low, the monomers tend to remain, which may result in a decrease in the molecular weight of the resulting polymer, whereas if the monomer concentration is too high, it may become difficult to control heat generation.

[0052] The polymerization temperature can be set appropriately depending on the type of monomer and the type of polymerization solvent, and is, for example, 50° C. to 120° C. The polymerization time can be set appropriately depending on the type of polymerization initiator and the polymerization temperature, and for example, when t-butyl peroxyneodecanoate is used as the polymerization initiator, a polymerization time of about 6 hours is suitable when polymerization is carried out at a polymerization temperature of 75° C.

[0053] The polymer obtained as described above may be used as a polymer solution as it is, or may be isolated by adding an alkali adsorbent or the like to the reaction solution after the polymerization reaction, as necessary, to remove part of the metal contained in the polymer and adjust the content thereof, and then subjecting the polymer to filtration, purification, and drying under reduced pressure.

[0054] <Surface conditioner> The surface conditioner according to the present invention may contain any of the polymers described above. Therefore, it may consist solely of the polymer, or it may contain other surface conditioners and / or other components containing components other than the polymer as active ingredients. Examples of other surface conditioners include silicone-based resins, acrylic silicone-based resins, and acrylic-based resins. Examples of other components include non-reactive resins (plasticizers, low-stress agents, etc.), antioxidants, UV absorbers, fillers, etc. The other surface conditioners and other components may be used alone or in combination of two or more. The content of the other surface conditioners and other components, if any, can be appropriately determined depending on the intended use. Since the polymer described above does not contain fluorine atoms, a surface conditioner that does not contain fluorine raw materials and has low environmental impact can be provided by ensuring that the other surface conditioners and other components do not contain fluorine raw materials. Furthermore, although a surface conditioner containing the polymer described above does not contain fluorine raw materials, it can impart leveling properties comparable to those of conventional fluorine-based surface conditioners to resin compositions, such as the curable resin composition described below, and is therefore suitable as a resin leveling agent. Furthermore, since the polymer contains a metal within a predetermined range, insoluble matters are not precipitated in solvents contained in various compositions used in the resist and semiconductor fields, and elution of metals is suppressed during processes in which various compositions used in these fields are applied. Therefore, the polymer is suitable as a leveling agent for use in resists and semiconductor applications.

[0055] <Curable resin composition> The curable resin composition according to the embodiment of the present invention contains the above-described polymer and curable resin. The above-described polymer may be contained in the curable resin composition by using the above-described surface conditioner, or the polymer may be used as it is in the curable resin composition. In the curable resin composition, the content of the polymer is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, in terms of leveling properties and resistance to elution of metal components, relative to 100 parts by mass of the curable resin.

[0056] The curable resin usable in the curable resin composition according to the embodiment of the present invention is not particularly limited, and examples thereof include photoresist resins (photocurable resins, etc.). Only one type of curable resin may be used, or two or more types may be used in combination. In this specification, curable compounds that do not have resinous properties, such as low-molecular-weight polyfunctional acrylic monomers, are also referred to as curable resins. Examples of photocurable resins include resins having a vinyl group, a vinyl ether group, an allyl group, a maleimide group, a (meth)acryloyl group, etc. Examples of such resins include poly(meth)acrylic acid resins, polyvinyl ether resins, urethane acrylate resins, epoxy acrylate resins, polyester acrylate resins, alicyclic epoxy resins, and glycidyl epoxy resins. As the polyfunctional acrylic monomer, a monomer having a (meth)acryloyl group is preferred. Examples of polyfunctional acrylic monomers include bifunctional vinyl monomers such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexadiol di(meth)acrylate, and trimethylolpropane di(meth)acrylate; trifunctional vinyl monomers such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; and tetrafunctional or higher vinyl monomers such as pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0057] The curable resin composition according to the embodiment of the present invention may contain a polymerization initiator depending on the type of the curable resin, etc. The polymerization initiator is a compound that serves as a starting point for the polymerization reaction of the curable resin, and any known polymerization initiator can be used.

[0058] When a photocurable resin is used as the curable resin, a photopolymerization initiator can be used. When a photopolymerization initiator is used, the wavelength of the light to be irradiated is not particularly limited, but an initiator suitable for the wavelength can be selected and used. The photopolymerization initiators in the present invention can be used alone or in combination of two or more.

[0059] Examples of the photopolymerization initiator 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-1-propanone, 4,4'-bis(dimethylamino)benzophenone (Michler's 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; benzil derivatives such as benzil dimethyl ketal; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-2-methyl-4,5-di(m-methoxyphenyl)-2-methyl-4-methyl ... 2,4,5-triarylimidazole dimers such as 2-(o-phenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, and 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer; N-phenylglycine, N-phenylglycine derivatives, acridine derivatives such as phenylacridine; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)]; coumarin compounds such as 7-diethylamino-4-methylcoumarin; thioxanthone compounds such as 2,4-diethylthioxanthone; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; and the like can be used.

[0060] A solvent and other components may be added to the curable resin composition according to the embodiment of the present invention, as long as the effects of the present invention are not impaired.

[0061] Known solvents can be used as the solvent. 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 solvents may be used in combination. When a solvent is used, the content is preferably 40 to 400% by weight, more preferably 150 to 300% by weight, based on the curable resin.

[0062] Examples of other components include heat resistance improvers, development aids, inorganic fine particles, coupling agents, fillers, curing agents, plasticizers, polymerization inhibitors, antioxidants, antifoaming agents, viscosity modifiers, and pigments. One or more of these other components may be used alone, or two or more may be used in combination. The content of these other components is preferably 0 to 20% by weight, more preferably 0 to 15% by weight, and even more preferably 0 to 10% by weight, based on the total weight of the curable resin composition.

[0063] The curable resin composition according to an embodiment of the present invention can be obtained by appropriately mixing the above-described polymer or surface conditioner, the above-described curable resin, and, if necessary, the above-described solvent and / or other components. The production method is not particularly limited, and examples thereof include a method of mixing or dispersing the above-described components using various mixers or dispersers. The method of adding each component is not particularly limited, and all components may be added and mixed simultaneously, or some components may be added and mixed in their entirety first, and then the remaining components may be added and mixed in their entirety or in portions, or other addition methods may be used. The order of addition and working conditions are not particularly limited, and known methods may be used.

[0064] Since the curable resin composition contains the above-mentioned polymer, there is no precipitation of insoluble matter, it has good leveling properties, and it is possible to suppress elution of metals during processes in which various compositions used in the resist field or the semiconductor field are applied.

[0065] <Cured film> A cured film can be obtained by curing the curable resin composition. The cured film can be obtained by various known methods. For example, a curable resin composition can be applied to the surface of a substrate to form a coating film, and then the curable resin can be cured to obtain a cured film. The method for applying the curable resin composition is not particularly limited, and examples include methods 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 to a substrate and then performing steps such as drying, pre-baking, photo-curing, developing, rinsing, and post-baking as appropriate, depending on the type of curable resin. The curing conditions for the curable resin can be determined appropriately depending on the type and blending ratio of each component. For example, for photo-curable resins, the heating conditions in the drying and pre-baking steps can be, for example, 50 to 120°C for 1 to 60 minutes. In the photo-curing step, ultraviolet rays such as i-line, h-line, and g-line, ArF laser, KrF laser, etc., can be used as the exposure light source. In the photocuring step, the coating film of the curable resin composition containing the photocurable resin may be exposed to light through a mask having a predetermined pattern.

[0066] The cured film, which is a coating film formed after curing using the curable resin composition having the above-mentioned good leveling properties, has a small and good surface roughness (Pa) of the cured film surface, similar to that of the case containing a conventional fluorine-based surface conditioner, and is also less susceptible to elution of metal components. These properties can be evaluated by the evaluation methods described in the Examples section below. [Example]

[0067] Hereinafter, the embodiments of the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0068] (Synthesis Example 1-1): Synthesis of compound (a-1) represented by the following formula (a-1) In a four-neck flask (500 mL) equipped with a condenser, 725 g (2.55 mol) of stearic acid (NOF Corporation, "NAA-180") and 310 g (5.10 mol) of monoethanolamine were placed. Nitrogen gas was introduced into the resulting reaction solution to replace the atmosphere inside the reaction vessel with nitrogen. The reaction solution was then heated to 150°C while being stirred, and the reaction was initiated. The reaction was then continued for 8 hours, and the completion of the reaction was confirmed. 1 The reaction mixture was confirmed by 1 H NMR (proton nuclear magnetic resonance). After that, the remaining monoethanolamine was distilled off to obtain the target compound (a-1).

[0069] [ka]

[0070] (Synthesis Example 1-2): Synthesis of Monomer (A-1) Monomer (A-1) was synthesized with reference to the method described in JP-A-2005-502698. Specifically, 196 g of compound (a-1) obtained in Synthesis Example 1-1, 260 g (3.02 mol) of methyl acrylate, 9.12 g (2% by mass based on the reaction mixture) of a catalyst (zirconium (IV) acetylacetonate), and 0.62 g of stabilizers (Irganox 1076 and 0.012 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl) were placed in a four-neck flask (500 mL) equipped with a condenser, and transesterification reaction was carried out at 70 to 90°C to synthesize Monomer (A-1).

[0071] (Synthesis Example 2-1): Synthesis of compound (a-2) represented by the following formula (a-2) Compound (a-2) was obtained in the same manner as in Synthesis Example 1-1, except that the raw material stearic acid was changed to the same molar amount of lauric acid.

[0072] [ka]

[0073] (Synthesis Example 2-2): Synthesis of Monomer (A-2) Monomer (A-2) was obtained in the same manner as in Synthesis Example 1-2, except that the raw material was changed from 196 g of compound (a-1) to 146 g of compound (a-2), and the amount of catalyst (zirconium (IV) acetylacetonate) was changed to 8.12 g.

[0074] (Synthesis Example 3-1): Synthesis of compound (a-3) represented by the following formula (a-3) Compound (a-3) was obtained in the same manner as in Synthesis Example 1-1, except that the raw material stearic acid was changed to the same molar amount of behenic acid.

[0075] [ka]

[0076] (Synthesis Example 3-2): Synthesis of Monomer (A-3) Monomer (A-3) was obtained in the same manner as in Synthesis Example 1-2, except that the raw materials were changed from 196 g of compound (a-1) to 223 g of compound (a-3), and the amount of catalyst (zirconium (IV) acetylacetonate) was changed to 9.65 g.

[0077] (Synthesis Example 4-1): Synthesis of compound (a-4) represented by the following formula (a-4) Compound (a-4) was obtained in the same manner as in Synthesis Example 1-1, except that the raw material stearic acid was changed to the same molar amount of acetic acid.

[0078] [ka]

[0079] (Synthesis Example 4-2): Synthesis of Monomer (A-4) Monomer (A-4) was obtained in the same manner as in Synthesis Example 1-2, except that the raw materials were changed from 196 g of compound (a-1) to 79 g of compound (a-4), and the amount of catalyst (zirconium (IV) acetylacetonate) was changed to 6.77 g.

[0080] (Synthesis Example 5-1): Synthesis of Compound (a-5) Represented by the Following Formula (a-5) Compound (a-5) was obtained in the same manner as in Synthesis Example 1-1, except that the raw material stearic acid was changed to the same molar amount of caprylic acid.

[0081] [ka]

[0082] (Synthesis Example 5-2): Synthesis of Monomer (A-5) Monomer (A-5) was obtained in the same manner as in Synthesis Example 1-2, except that the raw materials were changed from 196 g of compound (a-1) to 112 g of compound (a-5), from 260 g of methyl acrylate to 302 g of methyl methacrylate, and the amount of catalyst (zirconium (IV) acetylacetonate) was changed to 8.28 g, and the transesterification reaction was carried out at 10 to 120°C.

[0083] (Synthesis Example 6-1): Synthesis of compound (a-6) represented by the following formula (a-6) Compound (a-6) was obtained in the same manner as in Synthesis Example 1-1, except that the raw material stearic acid was changed to the same molar amount of 2-ethylhexanoic acid.

[0084] [ka]

[0085] (Synthesis Example 6-2): Synthesis of Monomer (A-6) Monomer (A-6) was obtained in the same manner as in Synthesis Example 1-2, except that the raw material was changed from 196 g of compound (a-1) to 112 g of compound (a-6) and the amount of catalyst (zirconium (IV) acetylacetonate) was changed to 7.44 g.

[0086] Regarding the monomers (A-1) to (A-6) which are embodiments of the monomer (A) obtained in each synthesis example, R 1 ~R 3 The compound names are summarized in Table 1.

[0087] [Table 1]

[0088] Regarding the monomers (B-1) to (B-4) which are embodiments of the monomer (B) used in the polymerization examples described later, R 4 , R 5 , AO, the average number of moles of AO added n, compound names, and abbreviations are summarized in Table 2.

[0089] [Table 2]

[0090] (Polymerization Example 1) A 500 mL beaker was used to mix 30.0 g of monomer (A-1), 70.0 g of PME-400 (product name: Blenmar PME-400, manufactured by NOF Corporation) as monomer (B-2), and 70.0 g of toluene, and the mixture was then heated to 40°C to dissolve, thereby obtaining a composition. Next, 70.0 g of propylene glycol monomethyl ether acetate 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 in the reaction vessel was raised to 75 ° C, and the above composition and 3.0 g of t-butyl peroxyneodecanoate were added dropwise over 2 hours, followed by a reaction at 75 ° C for 4 hours. 32 g of an alkali adsorbent (Kyoward (registered trademark) 700SL, manufactured by Kyowa Chemical Industry Co., Ltd.) was then added to the resulting polymerization solution and stirred at 40 ° C for 2 hours. The alkali adsorbent was then filtered, and the resulting polymerization solution was dried under reduced pressure at 120 ° C to obtain Polymer 1.

[0091] (Polymerization Example 2) Polymer 2 was obtained in the same manner as in Polymerization Example 1, except that the amount of Kyoward (registered trademark) 700SL was changed from 32 g to 21 g.

[0092] (Polymerization Example 3) Polymer 3 was obtained in the same manner as in Polymerization Example 1, except that the amount of Kyoward (registered trademark) 700SL was changed from 32 g to 16 g.

[0093] (Polymerization Example 4) Polymer 4 was obtained in the same manner as in Polymerization Example 1, except that the amount of Kyoward (registered trademark) 700SL was changed from 32 g to 11 g.

[0094] (Polymerization Example 5) Polymer 5 was obtained in the same manner as in Polymerization Example 1, except that the amount of Kyoward (registered trademark) 700SL was changed from 32 g to 6 g.

[0095] (Polymerization Example 6) Polymer 6 was obtained in the same manner as in Polymerization Example 2, except that the catalyst used in synthesizing Monomer (A-1) was changed from zirconium (IV) acetylacetonate to titanium acetylacetonate.

[0096] (Polymerization Example 7) Polymer 7 was obtained in the same manner as in Polymerization Example 4, except that the catalyst used in synthesizing Monomer (A-1) was changed from zirconium (IV) acetylacetonate to titanium acetylacetonate.

[0097] (Polymerization Example 8) Polymer 8 was obtained in the same manner as in Polymerization Example 5, except that the catalyst used in synthesizing Monomer (A-1) was changed from zirconium (IV) acetylacetonate to titanium acetylacetonate.

[0098] (Polymerization Example 9) Polymer 9 was obtained in the same manner as in Polymerization Example 2, except that the catalyst used in synthesizing Monomer (A-1) was changed from zirconium (IV) acetylacetonate to iron (III) acetylacetonate.

[0099] (Polymerization Example 10) Polymer 10 was obtained in the same manner as in Polymerization Example 4, except that the catalyst used in synthesizing Monomer (A-1) was changed from zirconium (IV) acetylacetonate to iron (III) acetylacetonate.

[0100] (Polymerization Example 11) Polymer 11 was obtained in the same manner as in Polymerization Example 3, except that the amount of t-butyl peroxyneodecanoate added was changed from 3.0 g to 10 g.

[0101] (Polymerization Example 12) Polymer 12 was obtained in the same manner as in Polymerization Example 3, except that the amount of t-butyl peroxyneodecanoate added was changed from 3.0 g to 0.5 g.

[0102] (Polymerization Examples 13 to 24) Polymers 13 to 24 were obtained in the same manner as in Polymerization Example 3, except that each component was added so as to achieve the compounding ratios shown in Tables 3 and 4 (in Tables 3 and 4, the unit of the monomer compounding amount is parts by mass, and the unit of the metal content is ppm by mass relative to the total of Monomer A / A' and Monomer B, 100% by mass).

[0103] (Polymerization Examples 25 and 26) Polymers 25 and 26 were obtained in the same manner as in Polymerization Example 3, except that the components were added in the blending ratios shown in Table 4 and the treatment with Kyoward (registered trademark) 700SL was not carried out.

[0104] (Polymerization Example 27) Polymer 27 was obtained in the same manner as in Polymerization Example 1, except that Kyoward (registered trademark) 700SL was not used.

[0105] [Measurement of weight average molecular weight] The weight average molecular weight of each of Polymers 1 to 27 obtained in Polymerization Examples 1 to 27 was determined by gel permeation chromatography (GPC) under the following conditions. Equipment: Tosoh Corporation, HLC-8220 Column: Shodex LF-804 Standard material: polystyrene Eluent: THF (tetrahydrofuran) Flow rate: 1.0mL / min Column temperature: 40℃ Detector: RID (refractive index detector)

[0106] [Metal content measurement] For each of Polymers 1 to 27 obtained in Polymerization Examples 1 to 27, the mass-based metal content relative to 100 mass% of the total of Monomer A / A' and Monomer B was measured and calculated using an inductively coupled plasma mass spectrometer (ICP-MS).

[0107] The monomers, metal contents, and weight average molecular weights of polymers 1 to 27 are shown in Tables 3 and 4. Monomer A' used in Polymerization Examples 25 and 26 and Monomer C used in Polymerization Examples 23 and 24 shown in Tables 3 and 4 are shown below. VA: Behenyl acrylate (product name: Blenmar VA, manufactured by NOF Corporation) PDMSMA: Polydimethylsiloxane with methacryloyl groups (product name: Silaplane FM-0711, manufactured by JNC Corporation) BA: Butyl acrylate (Mitsubishi Chemical Corporation) VP: N-vinylpyrrolidone (Nippon Shokubai Co., Ltd.)

[0108] [Table 3]

[0109] [Table 4]

[0110] Example 1 <Synthesis of curable resin (photoresist resin A)> In a 300 mL beaker, 16.5 g of methacrylic acid (product name: MAA, manufactured by Kuraray Co., Ltd.), 84.0 g of n-butyl methacrylate (product name: Monomer n-BMA, manufactured by Kuraray Co., Ltd.), 42.0 g of dicyclopentanyl methacrylate (product name: FA-513M, manufactured by Hitachi Chemical Co., Ltd.), 22.5 g of 4-hydroxymethyl acrylate (product name: PH-OH, manufactured by NOF Corporation), and 125 g of propylene glycol monomethyl ether (product name: PM, manufactured by Daicel Corporation) were mixed and then cooled on ice. 7.5 g of 2,2′-azobis(2,4-dimethylvaleronitrile) (product name: V-65, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to obtain a monomer composition. Next, 100 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 flask was heated to 75°C, and the above composition was added dropwise over 3 hours. After that, the mixture was reacted at 75°C for 4 hours, and the solvent was dried under reduced pressure to obtain photoresist resin A.

[0111] <Preparation of Curable Resin Composition> A curable resin composition was obtained by mixing 20 parts by mass of the photoresist resin A described above as the curable resin, 10 parts by mass of dipentaerythritol hexaacrylate ("Light Acrylate DPE-6A" manufactured by Kyoeisha Chemical Co., Ltd.) as a polyfunctional acrylic monomer, 2 parts by mass of a photopolymerization initiator (BASF Corporation, Irgacure 907, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone), 70 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and 1 part by mass of polymer 1 as a surface conditioner. The following evaluations were performed using polymer 1 used as a surface conditioner and the obtained curable resin composition.

[0112] <Preparation of cured film> 1.0 g of the prepared curable resin composition was applied to a copper plate using a bar coater (RDS 32), and then dried on a hot plate at 60°C for 10 minutes and then at 80°C for 30 minutes to form a coating film of the curable resin composition. The obtained coating film was irradiated with 400 mJ / cm2 of an ultra-high pressure mercury lamp through a mask.2 The resulting cured film was subjected to the following evaluations of leveling ability and elution of metal components.

[0113] <Turbidity> To 1 g of polymer, 20 g each of propylene glycol monomethyl ether acetate (PEGMA), propylene glycol monomethyl ether (PM), and a 50 / 50 (wt%) propylene glycol monomethyl ether (PM) / water mixed solvent were added as surface conditioners. The mixture was stirred at 40°C for 1 hour, then allowed to stand at room temperature for 5 minutes, and the turbidity of the liquid was evaluated using a portable turbidity meter TN100IR. The turbidity (NTU) was evaluated according to the following criteria. The lower the turbidity, the less likely it is that insoluble matter will precipitate in the solvent. ◎, ○, and △ are evaluated as good. ◎: Less than 10 NTU ○: 10NTU or more, less than 50NTU △: 50NTU or more, less than 250NTU ×:250NTU or more

[0114] <Leveling ability> The surface roughness of the obtained cured film was measured using a stylus surface roughness measuring instrument (DektakXT, manufactured by BRUKER). The arithmetic mean roughness (Pa) was evaluated according to the following criteria. The smaller the Pa value, the smaller the surface irregularities and the higher the smoothness. ◎, ○, and △ are evaluated as good. ◎: Less than 0.15 μm ○: Less than 0.25 μm, 0.15 μm or more △: Less than 0.40 μm, 0.25 μm or more ×: 0.40μm or more

[0115] <Metal elution> 1.0 g of the obtained cured film was immersed in 10 g of ion-exchanged water at 80°C for 1 hour, and the metal content eluted into the ion-exchanged water was measured using an inductively coupled plasma mass spectrometer (ICP-MS, manufactured by Aglent, product name Agilent 8900 triple quadrupole ICP-MS). The eluted metal content was evaluated according to the following criteria. The smaller the metal content, the less eluted the amount could be evaluated. ◎, ○, and △ were evaluated as good. ◎: Less than 1 ppb ○: 1 ppb or more and less than 100 ppb △: 100 ppb or more and less than 500 ppb ×: 500 ppb or more

[0116] (Examples 2 to 24, Comparative Examples 1 to 3) Curable resin compositions were prepared in the same manner as in Example 1, except that the formulations shown in Tables 5 and 6 were used, and cured films were formed and evaluated.

[0117] The evaluation results of Examples 1 to 24 and Comparative Examples 1 to 3 are shown in Tables 5 and 6.

[0118] [Table 5]

[0119] [Table 6]

[0120] As shown in Tables 5 and 6, when a curable resin composition containing a predetermined polymer composed of predetermined constituent monomers and containing a metal within a predetermined range is used as a surface conditioner, the evaluation results for turbidity, leveling ability, and metal elution are all good. Therefore, it is clear that the predetermined polymer is suitable for surface conditioners, particularly leveling agents, used in resists and semiconductor applications. On the other hand, Comparative Example 1 used behenyl acrylate, which has a different structure from the above-mentioned predetermined monomer (A), and the turbidity in PM and in a PM / water=50 / 50 mixed solvent was poor. Comparative Example 2 used PDMSMA, which has a different structure from the above-mentioned predetermined monomer (A), and the turbidity in a PM / water=50 / 50 mixed solvent was poor. In Comparative Example 3, Kyoward (registered trademark) 700SL was not used, and the metal content was higher than the above-mentioned predetermined range, so the evaluation of metal elution was poor.

Claims

1. A polymer comprising, as constituent monomers, a monomer (A) represented by the following formula (1) and a monomer (B) represented by the following formula (2), the polymer containing 0.001 ppm to 100 ppm of a metal by mass relative to 100% by mass of the total of the monomers (A) and (B), and the polymer having a weight average molecular weight of 3,000 to 3,000,000: 【Chemistry 1】 (In formula (1), R １ represents a hydrogen atom or a methyl group, and R ２ represents an alkylene group having 1 to 4 carbon atoms, and R ３ CO- has 2 to 30 carbon atoms, and R ３ represents an acyl group of an aliphatic hydrocarbon group.) 【Chemistry 2】 (In formula (2), R ４ , R ５ each independently represents a hydrogen atom or a methyl group, AO is selected from oxyalkylene groups having 2 to 4 carbon atoms, and n represents the average number of moles of oxyalkylene groups added and is a number from 1 to 100.

2. 2. The polymer according to claim 1, wherein the metal is at least one selected from the group consisting of iron, titanium, and zirconium.

3. A surface conditioner comprising the polymer according to claim 1 or 2.

4. 3. A curable resin composition comprising the polymer according to claim 1 or 2 and a curable resin, the curable resin composition containing 0.01 to 20 parts by mass of the polymer per 100 parts by mass of the curable resin.

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