TW201441363A - Deformer, surfactant composition, coating composition, and resist composition - Google Patents

Abstract

The purpose of the present invention is to provide a defoaming agent with greatly improved defoaming ability, without any adverse effect on surface smoothness, and a surfactant composition, a coating composition, and a resist composition containing the defoaming agent. Provided are a defoaming agent, characterized by being obtained through Michael addition of 2 to k moles of a compound (a2) having a fluorinated alkyl group and active hydrogen, to 1 mole of a compound (a1) having a number k (k is equal to 2 or greater) of (meth)acryloyl groups per molecule; a surfactant composition containing the defoaming agent and a fluorine based surfactant; a coating composition the defoaming agent and a fluorine based surfactant; and a resist composition the defoaming agent and a fluorine based surfactant.

Description

Defoamer, surfactant composition, coating composition and photoresist composition

The present invention relates to an antifoaming agent which does not adversely affect surface smoothness with respect to a fluorine-based surfactant and a leveling agent such as a photoresist for a semiconductor, and can greatly improve the defoaming property. Further, it relates to a surfactant composition, a coating composition, and a photoresist composition comprising the antifoaming agent.

A fluorine-based surfactant composed of a fluorine-based polymer can be used as a leveling agent for paints and resins because of a decrease in surface tension. On the other hand, the fluorine-based surfactant generally has a drawback that the foaming property is remarkably improved and the formed foam does not easily disappear. In the aqueous system, generally, as a method for reducing foaming, a method of adding an aqueous antifoaming agent such as a polyoxymethylene system is known. However, these aqueous antifoaming agents have a problem that the effect is extremely small in an organic solvent system having a large solubility. In addition, as for the organic solvent-based antifoaming agent, the antifoaming agent may cause coating defects such as cissing and uneven particles on the coating film, and it is desired that development does not adversely affect coating properties. An antifoaming agent that imparts excellent defoaming properties. As an antifoaming agent which does not cause coating defects such as shrinkage, uneven particles, etc., and imparts excellent defoaming property, for example, α, ω-bis(fluorinated alkylsulfonylamino)alkane and/or α-fluorinated alkylsulfonylamino, omegafluorinated alkylcarbonylaminoalkane and/or di(fluorinated) An antifoaming agent composed of an alkylcarbonylamino)alkane and containing a fluorine atom (for example, refer to Patent Document 1). However, the antifoaming agent disclosed in Patent Document 1 is almost incapable of expecting a defoaming effect when it is added to a solvent-based coating composition or a photoresist composition containing a surfactant.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 6-192689

The problem to be solved by the present invention is to provide an antifoaming agent and a coating composition and a photoresist composition using the same, which do not adversely affect surface smoothness, and can greatly improve the defoaming property thereof. .

The inventors of the present invention conducted a review in order to solve the above problems, and found that Michael addition is utilized by a (meth) acrylonitrile group of a polyfunctional (meth) acrylate. The compound obtained by adding a fluorinated alkyl group to the reaction can be used as an antifoaming agent, which does not adversely affect surface smoothness, and can greatly improve its defoaming property, and is utilized by the defoaming agent. The coating composition and the photoresist composition are used to obtain a coating composition excellent in defoaming property, a photoresist composition, and the like, so that the present invention can be completed.

That is, the present invention provides an antifoaming agent characterized by having (in this case, k is 2 or more) a (meth)acryl fluorenyl compound (a1) in one molecule of 1 mol, Meco can be obtained by adding 2~k mole of compound (a2) having a fluorinated alkyl group and an active hydrogen.

Further, the present invention provides a surfactant composition comprising the antifoaming agent and a fluorine-based surfactant.

Furthermore, the present invention provides a coating composition comprising the antifoaming agent and a fluorine-based surfactant.

Furthermore, the present invention provides a photoresist composition comprising the antifoaming agent and a fluorine-based surfactant.

According to the present invention, an antifoaming agent capable of reducing the foaming property of various fluorine-based surfactants can be provided. Moreover, since the antifoaming agent of the present invention can maintain the leveling property of the fluorine-based surfactant and suppress the occurrence of bubbles, it can be suitably used for a coating composition or a photoresist composition.

[Formation of the Invention]

The antifoaming agent of the present invention is a compound (a1) having k (here, k is 2 or more) (meth)acryloyl group in one molecule of 1 mole, and a keke addition 2 to k mole It is composed of a compound (a2) having a fluorinated alkyl group and an active hydrogen. In the case of the compound (a1) methacrylate compound (a2), even in the case of the 1 mol compound (a1), the addition of less than 2 mol (a2) is caused by the bubble of the surfactant. Defoaming agent with insufficient defoaming effect, so Not good.

Here, in the case where the compound (a1) used in the present invention is a mixture of compounds having various numbers of (meth) acrylonitrile groups, the compound (a1) has a (meth) acrylonitrile group. The number refers to the number of (meth) acrylonitrile groups which the compound has.

Since the defoaming effect of the bubble of the surfactant is excellent and the defoaming agent for the cost of the distillation of the unreacted raw material such as the unreacted compound (a2) is suppressed, the k is preferably 2~40, more preferably 2~20, even better 3~20, especially good 4~20. Here, in the case where a mixture of compounds having various k values is used as the compound (a1), the average value of the (meth)acryl fluorenyl group which one molecule has in the mixture is taken as k.

In the present invention, the (meth) acrylonitrile group is collectively referred to as an acryl fluorenyl group and a methacryl fluorenyl group. Further, all of the hydrogen atoms in the fluorinated alkyl-based alkyl group are substituted with a fluorine atom (perfluoroalkyl group) and a hydrogen atom of a part of the alkyl group is replaced by a fluorine atom (for example, HCF ₂ CF ₂ CF). ₂ CF ₂ -etc.) Further, those containing an oxygen atom in the fluorinated alkyl group (for example, CF ₃ -(OCF ₂ CF ₂ ) ₂ - or the like) are also included in the definition.

The antifoaming agent of the present invention is obtained by a Michael addition reaction of an active hydrogen group to a (meth) acrylonitrile group, specifically, k in one molecule of 1 mole (here, k is a compound (a1) of (meth) propylene fluorenyl group of 2 or more), which is added to a fluorinated alkane having a carbon atom number of 1 to 6 directly bonded by a fluorine atom by using a methic acid addition reaction The base and the active hydrogen compound (a2) are obtained. This reaction is an addition reaction, and therefore, there is no compound which is formed as a by-product due to the reaction, and the reaction conditions described later may also be in the temperature. And under conditions.

The compound (a1) to be used in the present invention is not particularly limited as long as it contains two or more (meth)acrylonyl groups in the molecule, and is appropriately selected depending on the intended use of the work, but is easily obtained. From the viewpoint of industrial raw materials and selection of mild reaction conditions and the like, the following general formula (3) is preferred.

Wherein R' is an alkyl group having 1 to 24 carbon atoms, an alkylcarbonyloxy group having 1 to 24 carbon atoms, CH ₂ =CHCO ₂ CH ₂ -, and CH ₂ =C(CH ₃ )CO ₂ CH ₂ - an alkylene group having a repeating number of 1 or more and having a terminal hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and having an alkyl group having 1 to 12 carbon atoms, Carboxyl group, or the following formula (4)

(wherein R ³ is a (meth) acrylonitrile group, and R ⁴ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl ester group having 1 to 18 carbon atoms or a carboxyl group, and t is 0 to 3; An integer, u is an integer of 0 to 3 and t + u = 3), R ¹ is a (meth) acryl fluorenyl group, and R ² is a hydrogen atom or an alkylcarbonyl group having 1 to 18 carbon atoms, and r is 2 or 3, s is 0 or 1 and r + s = 3. a compound (a1-1), a compound of the following formula (5), R ⁷ OL-OR ⁶ (5) [wherein, R ⁶ and R ⁷ are each a (meth) acryl fluorenyl group, and L is a carbon atom; The alkyl group having 1 to 18 alkyl groups, the repeating unit number of 1 to 30, the alkylene group having 1 to 4 carbon atoms, the cyclic hydrocarbon group having 3 to 100 carbon atoms or the aromatic hydrocarbon group having 6 to 100 carbon atoms. a compound (a1-2), a urethane (meth) acrylate (a1-3), a tris(meth) acrylate containing a cyanurate ring (a1-4), or Tris(meth)acrylate (a1-5).

Here, in the case where the alkoxy group is selected as the "L" in the formula (5), the alkoxy group may be used singly or in combination of two or more kinds. Here, in the case where two or more kinds of alkoxy groups are used as the "L", the number of repeating units means the total number of repeating units of each alkoxy group. Further, examples of the alkyleneoxy group having 1 to 4 carbon atoms include, for example, an oxidized ethyl group, an oxidized propyl group, an oxybutylene group, and a tetramethylene oxy group.

Among these, the compound (a1) having two or more (meth) acrylonitrile groups is particularly preferably the general formula (3) [only, R' is a linear one having a carbon number of 1 to 4. An alkyl group, CH ₂ =CHCO ₂ CH ₂ -, CH ₂ =C(CH ₃ )CO ₂ CH ₂ -, or an alkanol group having 1 to 3 carbon atoms, or a group represented by the formula (4) R ³ is a hydrogen atom or an alkylcarbonyl group having 1 to 12 carbon atoms. The compound shown.

The compound (a1) used in the present invention specifically includes the following compounds.

First, as a bifunctional (meth) acrylate, for example, 1,3-butanediol di(meth)acrylate (for example, SR-212 manufactured by Sartomer Co., Ltd.), 1,4- Diol di(meth)acrylate (for example, Viscoat #195 manufactured by Osaka Organic Chemical Co., Ltd.), 1,6-hexanediol di(meth)acrylate (for example, Kyoeisha Chemical Co., Ltd.) 1,6HX-A), ethylene oxide (hereinafter abbreviated as EO) modified 1,6-hexanediol di(meth)acrylate (for example, RCC13-361 manufactured by Sannopco Co., Ltd.), ring Chlorochloropropane (hereinafter abbreviated as ECH) is modified with 1,6-hexanediol di(meth)acrylate (for example, Kayarad R-167 manufactured by Nippon Kayaku Co., Ltd.), 1,9-nonane II Alcohol di(meth)acrylate (for example, Viscoat #215 manufactured by Osaka Organic Chemical Co., Ltd.), diethylene glycol di(meth)acrylate (for example, Blemmer ADE-100 manufactured by Nippon Oil & Fat Co., Ltd.), ECH modified hexahydrophthalic acid di(meth) acrylate (for example, Denacol acrylate DA-722 manufactured by Changchun Chemical Co., Ltd.), hydroxytrimethylacetic acid neopentyl glycol di(methyl) propyl Acid ester (Light aerylate HPP-A, etc. manufactured by Kyoeisha Chemical Co., Ltd.), neopentyl glycol di(meth)acrylate (for example, Kayarad NPGDA manufactured by Nippon Kayaku Co., Ltd.), EO modified Diol (meth) acrylate (for example, Photomer 4160 manufactured by Sannopco Co., Ltd.), propylene oxide (hereinafter abbreviated as PO), modified neopentyl glycol di(meth) acrylate (for example, chemical Sartomer Co., Ltd., SR-9003, etc.), stearic acid modified pentaerythritol di(meth)acrylate (for example, Aronix M-233, manufactured by Toagosei Co., Ltd.) Polyethylene glycol di(meth)acrylate (for example, Blemmer ADE-200 manufactured by Nippon Oil & Fat Co., Ltd.), polypropylene glycol di(meth)acrylate (for example, Blemmer ADP-200 manufactured by Nippon Oil & Fat Co., Ltd.) Etc.), polyethylene glycol-propylene glycol-polyethylene glycol di(meth)acrylate (for example, Blemmer ADC series manufactured by Nippon Oil & Fat Co., Ltd.), polytetramethylene diethylene glycol di(methyl) Acrylate (for example, Light acrylate PTMGA-250 manufactured by Kyoeisha Chemical Co., Ltd.) and polyethylene glycol di(meth)acrylate (for example, Light acrylate 3EG-A manufactured by Kyoeisha Chemical Co., Ltd.) , dimethylol dicyclopentane di(meth) acrylate (for example, IRR214 manufactured by Daicel UCB Co., Ltd.), tricyclodecane dimethanol di(meth) acrylate (for example, DIC Corporation) LUMICUREDCA-200), neopentyl glycol modified trimethylolpropane di(meth)acrylate (for example, Kayarad R-604 manufactured by Nippon Kayaku Co., Ltd.), triglycerol di(meth)acrylic acid Ester (for example, epoxy ester 80MFA manufactured by Kyoeisha Chemical Co., Ltd.).

As the trifunctional (meth) acrylate, for example, EO-modified glycerin acrylate (for example, New Frontier GE3A manufactured by Dai-Il Pharmaceutical Co., Ltd., etc.), PO-modified glycerin triacrylate (for example, , Beamset 720, manufactured by Arakawa Chemical Co., Ltd., pentaerythritol triacrylate (PETA) (for example, New Frontier PET-3, manufactured by Daiichi Kogyo Co., Ltd.), EO-modified phosphoric acid triacrylate (for example, Osaka Organic Chemistry) Viscoat 3A), trimethylolpropane triacrylate (TMTPA) (for example, New Frontier TMTP manufactured by Daiichi Kogyo Co., Ltd.), caprolactone modified trimethylolpropane triacrylate ( For example, Daicel UCB Co., Ltd. Ebecry12047 Etc.), HPA modified trimethylolpropane triacrylate (for example, Kayarad THE-330 manufactured by Nippon Kayaku Co., Ltd.), (EO) or (PO) modified trimethylolpropane triacrylate (for example) , LUMICURETA-300 manufactured by DIC Co., Ltd., New Frontier TMP-3P manufactured by Daiichi Pharmaceutical Co., Ltd., and alkyl modified dipentaerythritol triacrylate (for example, Kayarad D-330 manufactured by Nippon Kayaku Co., Ltd.) ), tris(propyleneoxyethyl)isocyanate (for example, Fancryl FA-731A manufactured by Hitachi Chemical Co., Ltd.), and the like.

Examples of the tetrafunctional (meth) acrylate include bis-trimethylolpropane tetraacrylate (DTMPTA) (for example, LUMICUREDTA-400 manufactured by DIC Co., Ltd.) and pentaerythritol ethoxy tetraacrylate (for example). , Diabeam UK-4154, manufactured by Mitsubishi Rayon Co., Ltd.), pentaerythritol tetraacrylate (PETTA) (for example, NK ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

Examples of the 5-functional or hexa-functional (meth) acrylate include, for example, dipentaerythritol hydroxypentaacrylate (for example, SR-399E manufactured by Sartomer Co., Ltd.), and alkyl-modified dipentaerythritol pentaacrylate (for example). , Kayarad D-310, manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate (for example, DAP-600 manufactured by DIC Co., Ltd.), dipentaerythritol penta and hexaacrylate ^. A polyfunctional monomer mixture (for example, LUMICUREDPA-620 manufactured by DIC Corporation) or the like.

Further, of course, the present invention is not limited by the specific examples. These systems may be used singly or in combination with a plurality of different (meth) acrylonitrile groups, and It can be used by mixing a plurality of compounds of different configurations. Further, the compound (a1) which is commercially available as a general product is a mixture of a compound having a different number of (meth)acrylonitrile groups as a main component. In the case of use, a compound having a desired number of (meth)acrylonitrile groups can be used by various purification methods such as chromatography and extraction, but the mixture can also be used as it is.

Further, as the compound (a1) used in the present invention, ethyl urethane (meth) acrylate (a1-2) can also be used. The method for producing the ethyl urethane (meth) acrylate (a1-2) is not limited in any way, and for example, it can be a hydroxyl group-containing (meth) acrylate having two or more (meth) acrylonitrile groups. (x1) is obtained by a complex addition reaction with an isocyanate compound (x2).

This reaction can also be carried out without a catalyst. From the viewpoint of reaction efficiency and the like, a reaction auxiliary agent such as a urethane-based catalyst or the like can also be used. As the urethane-catalyzed catalyst, for example, copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-dioxane [2.2] .2] octane, 2,6,7-trimethyl-1,4-dioxane[2.2.2]octane, etc., preferably relative to the hydroxyl group-containing (meth) acrylate used as a raw material (x1) is used in an amount of 0.01 to 10% by weight based on the total weight of the isocyanate compound (x2).

As the hydroxyl group-containing (meth) acrylate (x1), for example, 2-hydroxyethyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol hydroxy pentaacrylate, 2-hydroxy-3-propene oxime Propyl (meth) acrylate (for example, Blemmer GAM manufactured by Nippon Oil & Fat Co., Ltd.) and the like.

As the isocyanate compound (x2), any of an aromatic isocyanate compound, an aliphatic isocyanate compound, and an alicyclic isocyanate compound may be used, and examples thereof include toluene diisocyanate, methylphenyl diisocyanate, and nortenylene diisocyanate. Isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, adamantane diisocyanate, etc., the height of the glass transition temperature of the obtained cured product, the scratch resistance of the cured product, etc. In view of the above, it is preferred to have an alicyclic structure. For example, norformamidine diisocyanate, isophorone diisocyanate or adamantane diisocyanate is preferably used. In other words, the ethyl urethane (meth) acrylate (a1-2) is preferably a hydroxy group-containing (meth) acrylate (x1) having two or more (meth) acrylonitrile groups. Ethyl urethane (meth) acrylate obtained by reacting an isocyanate compound (x2) having an alicyclic structure. Further, a compound obtained by introducing a fluorinated alkyl group by addition of urethane (meth) acrylate (a1-2), or a compound having a hydroxyl group as the compound (a1-1) After the compound is introduced into the fluorinated alkyl group by a methine addition reaction, the compound is synthesized by reacting it with an isocyanate compound, and the reaction sequence is not particularly limited.

The compound (a1) used in the present invention has a high effect of improving the defoaming property, and does not cause shrinkage or uneven particles in the coating film. Therefore, it is preferably selected from the group consisting of dipentaerythritol hexaacrylate and pentaerythritol triacrylate. One or more compounds selected from the group consisting of pentaerythritol tetraacrylate, bis-trimethylolpropane tetraacrylate, polyoxypropylene diacrylate, and polyoxyethylene diacrylate.

Next, a compound having a fluorinated alkyl group and an active hydrogen (a2) Explain. From the viewpoint that the performance due to the fluorine atom can be effectively found, the fluorinated alkyl group is preferably a perfluoroalkyl group. Further, in the case of using a fluorinated alkyl group other than the perfluoroalkyl group, it is preferred to select the structure and type of the fluorinated alkyl group depending on the degree of performance and use which are required.

From the viewpoint of industrially easy and optional mild reaction conditions and the like, the compound (a2) is preferably a compound of the following formula (1): Rf(CH ₂ ) _m ZH (1)

Wherein m is an integer of 0 to 20, Rf is -C _n F _2n+1 (n is an integer of 1 to 20), and Z is a hydrogen atom or a nitrogen atom having an alkyl group having 1 to 24 carbon atoms, and oxygen An atom, a sulfur atom or a compound represented by -SO ₂ -NR- (R is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms), or the following formula (2)

[wherein, Y is an oxygen atom or a sulfur atom, p and q are each an integer of 1 to 4, and Rf and Rf ¹ are respectively -C _n F _2n+1 (n is an integer of 1 to 20), L and L ¹ Each of them is one or more groups selected from the group consisting of a carbonyl group, an alkyl group having a carbonyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. The compound shown.

In the formula (1), Z is a compound having a nitrogen atom having an alkyl group having 1 to 6 carbon atoms, a sulfur atom or -NR-SO ₂ - (R is an alkyl group having 1 to 6 carbon atoms) The compound (II) can be preferably obtained by a milder reaction condition. Further, in the general formula (2), Y is a sulfur atom, and it is preferred that the antifoaming agent of the present invention can be obtained by a milder reaction condition.

In Rf and Rf ¹ in the compound represented by the general formula (1) or the general formula (2), n is 4, 6 or 8 and the carbon number n of Rf in the general formula (1) is 4 or 6 Or 8 is preferable because it is an antifoaming agent which can obtain a coating material which is not easy to foam (low foaming property) and defoams in a short time even if it foams.

The antifoaming agent produced by using the compound represented by the above formula (1) or the formula (2) is used in the case of application to a photocurable composition, as the case of application, and optionally It is also advantageous in that the compatibility of other components used, the transparency of the obtained cured product, and the like, and the surface characteristics and optical characteristics due to the fluorine atom are also advantageous.

Examples of the compound represented by the above formula (1) include the following compounds, and these may be used singly or as a mixture of two or more kinds.

C ₄ F ₉ SO ₂ N(CH ₃ )H (a2-1)

C ₄ F ₉ SO ₂ N(C ₃ H ₇ )H (a2-2)

C ₄ F ₉ CH ₂ CH ₂ N(C ₈ H ₁₇ )H (a2-3)

C ₄ F ₉ CH ₂ CH ₂ SH (a2-4)

C ₆ F ₁₃ CH ₂ CH ₂ SO ₂ N(C ₈ H ₁₇ )H (a2-5)

C ₆ F ₁₃ CH ₂ CH ₂ SH (a2-6)

C ₆ F ₁₃ CH ₂ CH ₂ N(C ₄ H ₉ )H (a2-7)

C ₈ F ₁₇ CH ₂ CH ₂ SH (a2-8)

C ₈ F ₁₇ CH ₂ N(C ₃ H ₇ )H (a2-9)

C ₉ F ₁₉ CH ₂ CH ₂ SH (a2-10)

C ₁₀ F ₂₁ CH ₂ CH ₂ CH ₂ N(C ₃ H ₇ )H (a2-11)

C ₁₂ F ₂₅ CH ₂ CH ₂ SH (a2-12)

In addition, examples of the method for producing the compound represented by the above formula (2) include 2-hydroxysuccinic acid (hereinafter referred to as malic acid) and 2-mercaptosuccinic acid (hereinafter referred to as thiomalic acid). The method of reacting a fluorine-containing alkyl alcohol or a fluorine-containing alkyl mercaptan to form a diester is specifically exemplified by the following compounds.

The reaction of the compound (a1) with the compound (a2) can be carried out according to the usual method of the methacryl addition reaction, and it is not particularly necessary to have a fluorine atom, and it can be produced in the absence of a solvent or a solvent. . In the case of using a solvent, the compound (a1) and the compound (a2) are appropriately selected in consideration of solubility, boiling point, equipment used, and the like, and specific examples thereof include esters of ethyl acetate and butyl acetate. class Halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone (hereinafter, abbreviated as MEK), methyl isobutyl Ketones such as ketones (hereinafter abbreviated as MIBK); alcohols such as methanol, ethanol, and isopropanol; dimethylformamide, dimethylformamide, dimethylammonium, etc. The protic polar compound; an ether such as diethyl ether or tetrahydrofuran; or an aliphatic hydrocarbon such as hexane or heptane may be used singly or in combination of two or more kinds of solvents. Among these, esters, aromatic hydrocarbons, ketones, alcohols, ethers, dimethylformamide, dimethyl hydrazine, etc. are preferably used, and esters are particularly preferably used. Ketones, alcohols, ethers.

The reaction system may be carried out without a catalyst. However, in terms of reaction efficiency, a reaction auxiliary agent such as a catalyst may be appropriately selected. Examples of the reaction auxiliary agent include metal alkoxides such as sodium methoxide and sodium ethoxylate; trimethylamine, triethylamine, 1,4-dioxane-[2.2.2]-octane, and the like. Amines; metal hydrides such as sodium hydride, lithium hydride, etc.; benzyltrimethylammonium ^. Hydroxide, ammonium ^four. An ammonium salt such as a fluoride or a peroxide such as peracetic acid or the like is preferably a metal alkoxide, an amine or an ammonium salt, and particularly preferably an amine. The amount of the reaction auxiliary agent to be used is not particularly limited, but the compound (a1) used as a raw material is used in an amount of 0.01 to 50 mol%, preferably 0.1 to 20 mol%, based on 1 mol.

Further, thermal energy can be used alone or in combination by the compound (a1) and the compound (a2) to be used as a source of reaction activation energy. The reaction temperature is usually from 0 ° C to reflux temperature, preferably from 20 to 100 ° C, particularly preferably from 20 to 70 ° C. In the case of using a solvent or the like at the time of the reaction, the concentration of the solute is usually 2 to 90% by weight, preferably 20 to 80% by weight. The order of input as a reaction material is not particularly limited. The product obtained in this manner can also be purified and used by washing by extraction or the like, column chromatography, or the like, but it can also be used as it is. In particular, in the case where a compound having a large k value [the number of (meth) fluorenyl groups is used) in the compound (a1), it is usually not easy to control the addition position of the compound (a2), and the obtained defoaming agent becomes A mixture of various compounds having different addition positions, even in this case, does not need to be separated ^. A single substance can be taken out by refining, and a mixture of various compounds different in the position of the methine addition reaction can be used.

As described above, by the reaction of the compound (a1) with the compound (a2), without the need for a condensation reaction requiring a strong acid catalyst or the like, the present invention can be produced under simpler and milder conditions. Defoamer. In addition, it is possible to use a commercially available commercially available product or a variety of polyfunctional (meth) acrylates which are easy to synthesize as a starting material, and therefore, for the purpose of use of a coating composition containing an antifoaming agent and a photoresist composition, It is easy to appropriately adjust the structure or the fluorine atom content rate in one molecule for the purpose and the required characteristics, and it is a more effective production method.

Since the effect of improving the defoaming property is high and the compatibility is excellent, the weight average molecular weight of the antifoaming agent of the present invention is preferably from 300 to 20,000, more preferably from 500 to 10,000. Further, the number average molecular weight is preferably from 300 to 20,000, more preferably from 500 to 10,000.

In the present invention, the weight average molecular weight and the number average molecular weight are measured under the following conditions.

[GPC measurement conditions]

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation

Pipe column: "HHR-H" (6.0mm ID × 4cm) made by Tosoh Corporation + "TSK-GEL GMHHR-N" (7.8mm ID × 30cm) made by Tosoh Corporation + Tosoh Limited "TSK-GEL GMHHR-N" (7.8mm ID × 30cm) + "TSK-GEL GMHHR-N" (7.8mm ID × 30cm) manufactured by Tosoh Corporation + "TSK-GEL" manufactured by Tosoh Corporation GMHHR-N" (7.8mm ID × 30cm)

Detector: ELSD ("ELSD2000" by Alltech)

Data Processing: "GPC-8020 Model II Data Analysis Version 4.30" made by Tosoh Corporation

Measurement conditions: column temperature 40 ° C developing solvent tetrahydrofuran (THF) flow rate 1.0 ml / min

Sample: 1.0% by mass of a tetrahydrofuran solution was filtered through a micro-precision filter in terms of resin solid content.

Standard sample: The following monodisperse polystyrene having a molecular weight is conventionally used according to the measurement manual of "GPC-8020 Model II Data Analysis Version 4.30" described above.

(monodisperse polystyrene)

"A-500" made by Tosoh Corporation

"A-1000" made by Tosoh Corporation

"A-2500" made by Tosoh Corporation

"A-5000" made by Tosoh Corporation

"F-1" made by Tosoh Corporation

"F-2" made by Tosoh Corporation

Tosoh Corporation's "F-4"

"F-10" made by Tosoh Corporation

"F-20" made by Tosoh Corporation

Tosoh Corporation's "F-40"

"C-80" made by Tosoh Corporation

"C-128" made by Tosoh Corporation

"C-288" made by Tosoh Corporation

Tosoh Corporation's "F-550"

Since the effect of improving the defoaming property is high and the compatibility is excellent, the fluorine content in the antifoaming agent of the present invention is preferably in the range of 20 to 80% by mass, more preferably in the range of 25 to 70% by mass, and even more preferably. It is in the range of 30 to 60% by mass. Moreover, the fluorine content rate of the present invention is calculated from the mass ratio of fluorine atoms in the total amount of the raw materials prepared by using the surfactant of the present invention.

The surfactant composition of the present invention is characterized by comprising the antifoaming agent and a fluorine-based surfactant. As a fluorine-based surfactant, for example, Megaface F-171, Megaface F-172, Megaface F-173, Megaface F-176, Megaface F-177, Megaface F-141, Megaface F-142, Megaface F-143, Megaface F-144, Megaface R-30, Megaface F-437, Megaface F-475, Megaface F-479, Megaface F-482, Megaface F-554, Megaface F-560, Megaface F-561, Megaface F-780, Megaface F-781 [above is DIC (share) system], Fluorad FC430, Fluorad FC431, Fluorad FC171 [above is Sumitomo 3M (share) system], Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 [above, Asahi Glass Co., Ltd.] and the like.

Since the effect of improving the defoaming property is high and the state of the surface of the coating film is not deteriorated, the content of the antifoaming agent in the surfactant composition is preferably 100 parts by mass of the fluorine-based surfactant. 0.01 to 80 parts by mass, more preferably 0.1 to 50 parts by mass.

The coating composition of the present invention comprises the antifoaming agent of the present invention and a fluorine-based surfactant. The amount of the antifoaming agent to be added in the coating composition differs depending on the type of the coating resin, the coating method, and the intended film thickness. However, since the effect of improving the defoaming property is high, the state of the coating film is not deteriorated. The coating composition is preferably 0.000001 to 10 parts by mass, more preferably 0.00001 to 5 parts by mass, even more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the solid content.

The amount of the surfactant added in the coating composition varies depending on the type of the coating resin, the coating method, and the intended film thickness, but is preferably 100 parts by mass of the solid content of the coating composition. 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, still more preferably 0.01 to 2 parts by mass. When the surfactant of the present invention is added in this range, the surface tension can be sufficiently lowered, and the intended leveling property can be obtained, and the occurrence of defects such as foaming at the time of coating can be suppressed.

As the surfactant to be used herein, for example, a fluorine-based surfactant or the like can be preferably used.

By using the antifoaming agent and the fluorine-based surfactant of the present invention as an additive of a coating composition, smoothness (leveling property) can be obtained. And a coating composition having low foaming properties. As such a coating composition series, for example, various coating composition and photosensitive resin composition are mentioned.

Examples of the coating composition include petroleum resin paint, shellac paint, rosin paint, cellulose paint, rubber paint, paint paint, cashew resin paint, and oil vehicle. Coatings using natural resins such as paints; phenol resin coatings, alkyd resin coatings, unsaturated polyester resin coatings, amine based resin coatings, epoxy resin coatings, vinyl coatings, acrylic resin coatings, polyurethane coatings A synthetic resin coating such as a polyoxyxylene resin coating or a fluororesin coating.

Further, in addition to the above-described coating composition, the antifoaming agent of the present invention may be used as an active energy ray-curable composition as a coating composition. The active energy ray-curable composition contains an active energy ray-curable resin or an active energy ray-curable monomer as its main component. Further, the active energy ray-curable resin and the active energy ray-curable single system may be used singly or in combination.

The active energy ray-curable resin is, for example, a urethane (meth) acrylate resin, an unsaturated polyester resin, an epoxy (meth) acrylate resin, a polyester (meth) acrylate resin, An acrylic (meth) acrylate resin, a maleimide-containing resin, or the like, but in the present invention, in particular, from the viewpoint of transparency, low shrinkage, etc., urethane (A) is preferred. Base) acrylate resin.

The urethane (meth) acrylate resin used herein, which is obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound. A resin having a urethane bond and a (meth) acrylonitrile group.

Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, and decamethylene. Diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, nor formamidine diisocyanate, hydrogenated diphenylmethane Diisocyanate, hydrogenated toluene diisocyanate, hydrogenated dimethyl diisocyanate, hydrogenated tetramethyl dimethyl diisocyanate, cyclohexyl diisocyanate, etc., and as an aromatic polyisocyanate compound, a series of toluene diisocyanate, 4, 4'-diphenylmethane diisocyanate, benzodimethyl diisocyanate, 1,5-naphthalene diisocyanate, di-toluidine diisocyanate, benzene p-diisocyanate, and the like.

Examples of the hydroxyl group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. 4-hydroxybutyl (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono ( Mono(meth) acrylate of 2-alcohol such as methyl acrylate, hydroxytrimethylacetic acid neopentyl glycol mono (meth) acrylate; trimethylolpropane di(meth) acrylate, B Oxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di(meth) acrylate, glycerol di(meth) acrylate, bis(2-(methyl) a single or two of a 3-valent alcohol such as propylene methoxyethyl) hydroxyethyl iso-cyanurate a (meth) acrylate or a hydroxy-containing mono- and di(meth) acrylate which is a part of the alcoholic hydroxy group modified by ε-caprolactone; pentaerythritol tri(meth) acrylate, bis- a compound having a monofunctional hydroxyl group and a trifunctional or higher (meth)acrylinyl group such as trimethylolpropane tri(meth)acrylate or dipentaerythritol penta(meth)acrylate, or further by ε- Hydroxy-containing polyfunctional (meth) acrylate of this compound modified by caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate (meth) acrylate compound having an oxygen alkyl chain such as ester, polyethylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene butyl - (meth) acrylate compound having a block structure of an alkylene chain such as polyoxyl propyl mono (meth) acrylate; poly(ethylene glycol-tetramethyl diol) mono (methyl) (meth)acrylic acid ester of a randomly structured oxygen alkyl chain such as acrylate or poly(propylene glycol-tetramethyl glycol) mono(meth)acrylate And the like.

The reaction of the aliphatic polyisocyanate compound or the aromatic polyisocyanate compound and the hydroxyl group-containing acrylate compound can be carried out, for example, by a usual method in the presence of a urethane catalyst. The urethane-based catalyst can be used, and specific examples thereof include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; triphenylphosphine, triethylphosphine, and the like. Phosphine; organotin compound such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octylate; zinc octylate Organometallic compounds.

In the urethane acrylate resin, by hard The chemical conversion film is excellent in transparency, and is excellent in the sensitivity to the active energy ray, and is excellent in curability, and is particularly preferably obtained by reacting an aliphatic polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound.

Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of an α,β-unsaturated dibasic acid or an anhydride thereof, an aromatic saturated dibasic acid or an anhydride thereof, and a diol, as α, a β-unsaturated dibasic acid or an anhydride thereof, which is a series of maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloro-maleic acid, and the like Ester and the like. As the aromatic saturated dibasic acid or its anhydride, a series of tantalic acid, phthalic anhydride, isophthalic acid, p-nonanoic acid, nitrodecanoic acid, tetrahydrophthalic anhydride, endomethylene tetrahydroanthracene anhydride, halogenated phthalic anhydride, And such esters and the like. As an aliphatic or alicyclic saturated dibasic acid, a series of oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, glutaric acid, hexahydrophthalic anhydride, and the like, etc. . As a glycol series, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol , neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2 Further, 2-di-(4-hydroxypropoxydiphenyl)propane or the like may be used in the same manner, and an oxide such as a stretched ethyl oxide or a propylated oxide may be used in the same manner.

Next, as the epoxy vinyl ester resin, a series of epoxy groups such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, and cresol type epoxy resin are used. The reaction is carried out by reacting (meth)acrylic acid.

Also, as a maleimide-containing resin, a series of pairs a 2-functional maleimide-imidourethane ethyl ester compound obtained by ethylation of N-hydroxyethyl maleimide and isophorone diisocyanate, for cis-butyl A bifunctional maleimide ester compound obtained by esterification of enediethyleneimineacetic acid with polytetramethylene glycol, and tetra-oxidation of pentaerythritol hexanoic acid and pentaerythritol a 4-functional maleimide ester compound obtained by esterification with an ethyl addition product, and a polyfunctional maleic acid obtained by esterification of maleic acid imide acetic acid with a polyol compound An imidate compound or the like. These active energy ray-curable resins may be used singly or in combination of two or more.

Examples of the active energy ray-curable monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and a number average molecular weight. Polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, in the range of 150 to 1000, average number Polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butylene having a molecular weight of 150 to 1000 Alkanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, bisphenol A (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris Methyl propane di(meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (methyl) propyl Ethyl ester, propyl (meth) acrylate, butyl (A) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (A) Aliphatic alkyl (meth) acrylate of acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, etc.; glycerol (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (A) Acrylate, 2-butoxyethyl (meth) acrylate, 2-(diethylamino)ethyl (meth) acrylate, 2-(dimethylamino)ethyl (methyl) Acrylate, γ-(meth)acryloxypropyltrimethoxydecane, 2-methoxyethyl (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy Dipropylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate, phenoxy ethyl (meth) acrylate Phenoxydipropylene glycol (meth) acrylate, phenoxy poly Glycol (meth) acrylate, polybutadiene (meth) acrylate, polyethylene glycol - polypropylene glycol (meth) acrylate, polyethylene glycol - polybutylene glycol (meth) acrylate, Polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (methyl) Acrylate, isodecyl (meth) acrylate, methoxylated cyclotridecene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methyl Maleimide, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide, N-hexylbutylene Imine, N-octyl maleimide, N-dodecyl maleimide, N-stearyl maleimide, N-phenylbutylene Amine, N-cyclohexyl-cis-butene Dimethyleneimine, 2-m-butylenedimine, ethyl-ethyl carbonate, 2-m-butylenediamine, ethyl-propyl carbonate, 2-ethyl-(2-cis-butene Dimethyleneimine ethyl)carbamate, N,N-hexamethylenebissuccinimide, polypropylene glycol-bis(3-maleoximeimidopropyl)ether, double a maleimide such as (2-m-butylene iminoethyl) carbonate or 1,4-dimethyleneimine hexane.

Among these, in particular, from the viewpoint of excellent hardness of the cured coating film, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(methyl) is preferable. A bifunctional or higher polyfunctional (meth) acrylate such as acrylate or pentaerythritol tetra(meth)acrylate. These active energy ray-curable single systems may be used singly or in combination of two or more.

The active energy ray-curable composition can be a cured coating film by irradiating an active energy ray after coating the substrate. The active energy ray means free radiation such as ultraviolet rays, electron rays, alpha rays, beta rays, and gamma rays. In the case where the ultraviolet ray as the active energy ray is irradiated as the cured coating film, it is preferred to add a photopolymerization initiator to the active energy ray-curable composition to improve the hardenability. Further, if necessary, a photosensitizer may be added to improve the curability. On the other hand, in the case of using free radiation such as electron rays, α rays, β rays, and γ rays, even if no photopolymerization initiator and photo sensitizer are used, the curing is rapidly performed, and therefore, there is no particular need to add. Photopolymerization initiator and photo sensitizer.

As the photopolymerization initiator, a series of intramolecular splitting type photopolymerization initiators and hydrogen extraction (H-abstraction type) photopolymerization initiators are mentioned. As a series of intramolecular cracking type photopolymerization initiators, for example, diethoxyethyl benzene, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1- (4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1 -hydroxycyclohexyl-benzophenone, 2-methyl-2- Phytyl (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- An acetophenone compound such as phenylphenyl)-butanone; benzoin such as benzoin, benzoin methyl ether, benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenylphosphine oxide, double (2 a fluorenylphosphine oxide compound such as 4,6-trimethylbenzylidene)-phenylphosphine oxide; a benzyl group, a tolyl acetaldehyde ester or the like.

Examples of the hydrogen extraction type photopolymerization initiator include diphenyl ketone, o-benzylidene benzoic acid methyl-4-phenyldiphenyl ketone, and 4,4'-dichlorodiphenyl ketone. , hydroxydiphenyl ketone, 4-benzylidene-4'-methyl-disulfide phenyl, propenylated diphenyl ketone, 3,3',4,4'-tetra(t-butyl a diphenyl ketone compound such as oxycarbonyl)diphenyl ketone or 3,3'-dimethyl-4-methoxydiphenyl ketone; 2-isopropyl-9-oxysulfide 2,4-dimethyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 9-oxosulfur a compound; an aminodiphenyl ketone compound such as rice ketone or 4,4'-diethylaminodiphenyl ketone; 10-butyl-2-chloroacridone, 2-ethyl hydrazine 9,10-Phoenix, camphor and so on.

In the photopolymerization initiator, from the viewpoint of excellent compatibility between the active energy ray-curable resin and the active energy ray-curable monomer in the active energy ray-curable coating composition, 1-hydroxyl is preferred. Cyclohexyl benzophenone and diphenyl ketone, particularly preferably 1-hydroxycyclohexyl benzophenone. These photopolymerization initiators may be used singly or in combination of two or more.

Further, examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylsulfuryl urea, sodium diethyl dithiophosphate, and s-benzyl isosulfur. A sulfur compound such as benzyl isothiuronium-p-tosylate or the like.

The amount of the photopolymerization initiator and the photosensitizer to be used is preferably 0.01 to 20 parts by mass, more preferably 0.1%, per 100 parts by mass of the non-volatile component of the active energy ray-curable composition. ~15 parts by mass, more preferably 0.3 to 7 parts by mass.

Further, in the coating composition, an organic solvent or a coloring agent such as a pigment, a dye or a carbon; a cerium oxide, a titanium oxide, a zinc oxide, an aluminum oxide, a zirconium oxide, a calcium oxide or a calcium carbonate may be appropriately added as needed. Inorganic powder; higher fatty acid, propylene resin, phenol resin, polyester resin, polystyrene resin, urethane resin, urea resin, melamine resin, alkyd resin, epoxy resin, polyamide resin, poly Various resin micro-powders such as carbonate resin, petroleum resin, fluororesin (PTFE (polytetrafluoroethylene), etc.), polyethylene, polypropylene, etc.; antistatic agent, viscosity adjuster, light stabilizer, weathering stabilizer, heat stability Agent, antioxidant, rust inhibitor, slip agent, wax, gloss adjuster, mold release agent, compatibilizer, conductivity adjuster, dispersant, dispersion stabilizer, tackifier, anti-precipitant, polyoxane Or various additives such as a hydrocarbon surfactant.

The organic solvent is used for appropriately adjusting the viscosity of the solution of the coating composition, and particularly for coating the film, it is easy to adjust the film thickness. A series of organic solvents that can be used herein include aromatic hydrocarbons such as toluene, xylene, etc.; methanol, ethanol, isopropanol, t- An alcohol such as butanol; an ester such as ethyl acetate or propylene glycol monomethyl ether acetate; a ketone such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone. These solvents may be used singly or in combination of two or more.

Moreover, the coating method of the coating composition differs depending on the use, and examples thereof include, for example, a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, Knit coater, spray coater, wheel coater, spin coater, dipping, screen printing, spraying, applicator, bar coater, electrostatic coating, etc. The coating method, or a molding method using various molds, or the like.

The photosensitive resin composition described above changes the physical properties such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability of the resin by irradiation with light such as visible light or ultraviolet light. In the photosensitive resin composition, a photoresist composition (a photoresist composition, a color resist composition for a color filter, etc.) is also required to have a high degree of leveling property. In general, in photolithography for semiconductor or liquid crystal, a photoresist composition is generally applied by a spin coating on a ruthenium wafer or a glass substrate on which various metals are vapor-deposited so as to have a thickness of about 1 to 2 μm. In this case, the vibration of the coating film thickness is a deterioration of the quality of the semiconductor or the liquid crystal element, and the fluorine-based surfactant of the present invention can be used as an additive of the photosensitive resin composition by the height thereof. Since the leveling property is formed to form a more uniform coating film, productivity and high performance of semiconductors and liquid crystal elements are possible.

Next, the photoresist composition of the present invention will be described. The photoresist composition of the present invention is characterized by comprising the antifoaming agent of the present invention And fluorine-based surfactants. Usually, the photoresist composition is composed of the antifoaming agent of the present invention and a fluorine-based surfactant and a photoresist, and the photoresist comprises (1) an alkali-soluble resin and (2) a radiation-sensitive substance (photosensitive substance). ), (3) solvent, and (4) other additives as needed.

As the (1) alkali-soluble resin to be used in the photoresist composition of the present invention, for example, a resin which is soluble in an alkaline solution of a developer used in patterning of a photoresist is used. Examples of the alkali-soluble resin include, for example, an aromatic hydroxy compound selected from the group consisting of phenol, cresol, xylenol, resorcin, 1,3,5-benzenetriol, hydroquinone, and the like. At least one of a group-substituted or halogen-substituted aromatic compound, a phenol resin obtained by condensation with an aldehyde compound such as formaldehyde, acetaldehyde or benzaldehyde, o-vinylphenol, m-vinylphenol, p-vinylphenol a vinyl phenol compound such as α-methylvinylphenol, a polymer or copolymer of the halogen-substituted compound, or an acrylic or methyl group such as acrylic acid, methacrylic acid or hydroxyethyl (meth) acrylate. An acrylic polymer or copolymer, polyvinyl alcohol, or a part of a hydroxyl group of the above various resins, further introduced into a benzoquinonediazide group, a naphthacene azide group, an aromatic azide group, an aromatic cinnamyl group, or the like A radiation-sensitive resin such as a modified resin. These alkali-soluble resins may be used singly or in combination of two or more.

Further, as the alkali-soluble resin, a urethane resin containing an acidic group such as a carboxylic acid or a sulfonic acid in a molecule may be used, and the urethane resin may be used in combination with the above alkali-soluble resin. .

(2) radiation as a photoresist composition used in the present invention A line-sensitive substance (photosensitive substance) is obtained by mixing with an alkali-soluble resin, irradiating ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, ion lines, molecular lines, γ rays, and the like. A substance which changes the solubility of the developer of the alkali-soluble resin can be used.

Examples of the radiation-sensitive substance include a benzoquinonediazide-based compound, a diazo-based compound, a diazide-based compound, an onium salt compound, a halogenated organic compound, a mixture of a halogenated organic compound and an organometallic compound, and an organic acid. An ester compound, an organic acid decylamine compound, an organic acid quinone imine compound, and a poly(olefin oxime) compound described in JP-A-59-152.

Examples of the benzoquinonediazide compound include, for example, 1,2-benzobenzoquinone azide-4-sulfonate and 1,2-naphthacenequinonediazide-4-sulfonate. 1,2-naphthacenequinonediazide-5-sulfonate, 2,1-naphthacenequinonediazide-4-sulfonate, 2,1-naphthacenequinonediazide -5-sulfonate, other 1,2-benzobenzoquinone azide-4-sulfonic acid, 1,2-naphthacenequinonediazide-4-sulfonic acid, 1, 2-naphthacenequinonediazide-5-chlorosulfonic acid, 2,1-naphthacenequinonediazide-4-sulfonic acid, 2,1-naphthacenequinonediazide -5-sulfonic acid chloride of a benzoquinonediazide derivative such as chlorinated sulfonic acid.

As the diazonium compound, for example, a salt of a condensate of p-diazonium diphenylamine and formaldehyde or acetaldehyde, for example, hexafluorophosphate, tetrafluoroborate, perchlorate or periodate, and the above condensation The diazonium resin inorganic salt of the reaction product of the product, and the diazo resin organic salt of the reaction product of the condensate and the sulfonic acid described in the specification of US Pat. No. 3,300,309.

Examples of the azide-based compound and the diazide-based compound include azido-based ketone acid and diazidobenzylidene methylcyclohexanone, which are described in JP-A-58-203438. An azido-based compound or an aromatic diazide compound described in Japanese Patent Laid-Open No. 12, p1708-1714 (1983).

The halogenated organic compound can be used, for example, as a halide of an organic compound, and specific examples thereof include a halogen-containing oxydiazole compound and a halogen-containing three. Compound, halogen-containing acetophenone-based compound, halogen-containing diphenyl ketone-based compound, halogen-containing sulfonium-based compound, halogen-containing fluorene-based compound, halogen-containing thiazole-based compound, halogen-containing compound An azole compound, a halogen-containing triazole compound, a halogen-containing 2-pyrone compound, a halogen-containing aliphatic hydrocarbon compound, a halogen-containing aromatic hydrocarbon compound, another halogen-containing heterocyclic compound, a thiophenyl halogenated compound Various compounds such as compound compounds, further, for example, tris(2,3-dibromopropyl)phosphate, tris(2,3-dibromo-3-chloropropyl)phosphate, chlorotetrabromomethane, hexachlorobenzene, Hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether) tetrabromobisphenol A, Bis(chloroethyl ether) tetrachlorobisphenol A, tris(2,3-dibromopropyl)isocyanate, 2,2-bis(4-hydroxy-3,5-dibromophenyl) Use of propane or 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane as a compound of a halogen-based flame retardant, dichlorophenyltrichloroethane or the like as an organic A compound of a chlorine-based pesticide or the like.

Examples of the organic acid ester series include a carboxylate, a sulfonate, and the like. Further, as the organic acid amide series, carboxylic acid decylamine, sulfonate decylamine Wait. Further, examples of the organic acid bismuth imide include carboxylic acid quinone imine and sulfonium sulfinimide. These radiation-sensitive substances may be used singly or in combination of two or more.

In the photoresist composition of the present invention, the blending ratio of the radiation-sensitive substance is preferably in the range of 1 to 100 parts by mass, more preferably in the range of 3 to 50 parts by mass, per 100 parts by mass of the alkali-soluble resin. .

The (3) solvent series used as the photoresist composition of the present invention is, for example, acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, Ketones such as butyrolactone; methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, pentanol, heptanol, octanol, decyl alcohol, hydrazine Alcohols such as alcohol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, two Ethers such as ethers; glycol esters such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether; ethyl formate, formic acid Propyl ester, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, butyric acid Esters of ethyl ester, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate, etc.; 2-oxomethylpropionic acid, 2-oxoethylpropionic acid, 2-oxopropylpropionic acid, 2 a monocarboxylic acid such as oxybutylpropionic acid, 2-methoxymethylpropionic acid, 2-methoxyethylpropionic acid, 2-methoxypropylpropionic acid or 2-methoxybutylpropionic acid Acid esters; 赛路苏acetate, methyl sarprosone acetate, ethyl stilbene acetate, propyl ceramide acetate, butyl succinate acetate, etc. Terephthalate; propylene glycol such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol dimethyl ether, diethyl a diethylene glycol such as diol diethyl ether or diethylene glycol methyl ether; a halogenated hydrocarbon such as trichloroethylene, a fluorocarbon solvent, HCFC or HFC; a completely fluorinated solvent such as perfluorooctane; toluene An aromatic group such as xylene; a polar solvent such as dimethylacetamide, dimethylformamide, N-methylacetamide or N-methylpyrrolidone; The solvent described in (Organic Synthetic Chemistry Association, Ohmsha Corporation). These solvents may be used singly or in combination of two or more.

The amount of the antifoaming agent to be added in the photoresist composition of the present invention varies depending on the type of the photoresist composition, the coating method, the intended film thickness, and the like. However, since the effect of improving the defoaming property is high, the coating is not applied. In the photoresist composition, the photosensitive composition is preferably 0.000001 to 10 parts by mass, more preferably 0.00001 to 5 parts by mass, even more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the solid content.

The amount of the fluorine-based surfactant added in the coating composition differs depending on the type of the photoresist composition, the coating method, the intended film thickness, and the like, but in the photoresist composition, 100 parts by mass relative to the solid content. It is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, still more preferably 0.01 to 2 parts by mass. When the surfactant of the present invention is added in an amount in this range, the surface tension can be sufficiently lowered, and the intended leveling property can be obtained, and the occurrence of defects such as foaming at the time of coating can be suppressed.

As a coating method of the photoresist composition of the present invention, a series of methods such as spin coating, roll coating, dip coating, spray coating, blade coating, slit coating, curtain coating, gravure coating, and the like are employed. It is also possible to filter the photoresist composition by a filter before coating to remove solid impurities.

As described above, the antifoaming agent of the present invention is useful as a coating composition (a coating composition, a photosensitive resin composition, etc.) and an additive of a photoresist composition. Examples of the application of the antifoaming agent of the present invention include inks for gravure printing and inks for inkjet printing of hard coating materials such as liquid crystal displays, plasma displays, and organic EL displays (PDPs); and mobile phones; Frame coating or hard coating material; hard coating material for mobile phone screen; hard coating material for optical recording media such as CD, DVD, Blu-ray disc, etc. Hard for transfer film for insert molding (IMD, IMF) Coating materials; printing inks or coatings for various building materials such as cosmetic boards; coating materials for window glass for residential use; woodworking coatings for furniture; artificial ^. Coating material for synthetic leather; paint or coating material for various plastic molding products such as housing of home appliance; coating or coating material for FRP bathtub; color light for forming each pixel of RGB used for color filter for liquid crystal display A black resist that is used to form a black matrix; a photoresist used in semiconductor manufacturing; a photosensitive material for a lithographic printing plate (PS plate); a single-layer or multi-layer coating composition for other photo-processing processes, and the like. By adding the fluorine-based surfactant of the present invention to the coating composition, it is possible to exhibit excellent smoothness without pinholes, orange peel, no coating unevenness, and no shrinkage.

Furthermore, the antifoaming agent of the present invention improves the dispersibility of the fluororesin by the action of a fluorinated alkyl group when blended with a coating material or a coating material of a fluorine-containing resin, and is not only leveling property but also It is expected to function as a dispersant for fluororesin.

[Examples]

Hereinafter, the present invention will be described in detail in comparison with the comparative examples by exemplifying the examples of the present invention. In the example, "parts" and "%" are quality standards as long as they are not particularly limited.

Example 1 (defoamer of the present invention)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 40 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Tridecafluorootyl thiol and 1 g of triethylamine. Here, 10 g of dipentaerythritol hexaacrylate was dropped over 1 hour. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 6 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (1) of the present invention having a solid content of 100%. The antifoaming agent (1) had a number average molecular weight of 3,022 and a weight average molecular weight of 3,107. Further, the fluorine content was 51.8% by mass.

According to the analysis by NMR, the defoamer (1) is added to the average of 5.7 moles of 1,3-molar 3,3,4,4,5,5,6,6,7,7 in 1 mole of dipentaerythritol hexaacrylate. a compound of 8,8,8-tridecafluorooctanethiol.

Further, the analysis by ¹³ C-NMR was carried out under the following conditions.

[ ¹³ C-NMR measurement conditions]

Device: Japan Electronics (share) system AL-400

Solvent: chloroform-d1

Example 2 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 40 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 1 g of triethylamine. Spend 10g of pentaerythritol in 1 hour Triacrylate. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 6 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (2) of the present invention having a solid content of 100%. The antifoaming agent (2) had a number average molecular weight of 1,713 and a weight average molecular weight of 1,773. Further, the fluorine content was 51.5% by mass.

According to the analysis by NMR, the antifoaming agent (2) was added to the average of 2.9 moles of 3.9 moles of 3,3,4,4,5,5,6,6,7,7 in 1 mole of pentaerythritol triacrylate. A compound of 8,8,8-tridecafluorooctanethiol.

Example 3 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 41 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 1 g of triethylamine. It took 9 hours to drip 9 g of pentaerythritol tetraacrylate. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 6 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (3) of the present invention having a solid content of 100%. The antifoaming agent (3) had a number average molecular weight of 2,048 and a weight average molecular weight of 2,084. Further, the fluorine content was 52.8 mass%.

According to the analysis by NMR, the antifoaming agent (3) was added to the average of 4.0 moles of 3,3,4,4,5,5,6,6,7,7 in 1 mole of pentaerythritol tetraacrylate. A compound of 8,8,8-tridecafluorooctanethiol.

Example 4 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 38 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 1 g of triethylamine. It took 1 hour to drip 12 g of bis-trimethylolpropane tetraacrylate. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 6 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (4) of the present invention having a solid content of 100%. The antifoaming agent (4) had a number average molecular weight of 2,260 and a weight average molecular weight of 2,299. Further, the fluorine content was 49.7% by mass.

According to the analysis by NMR, the antifoaming agent (4) is added to the average of 3.9 moles of 3,3,4,4,5,5,6 in 1 mole of bistrifluoromethylolpropane tetraacrylate. A compound of 6,7,7,8,8,8-tridecafluorooctanethiol.

Example 5 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 59 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 2 g of triethylamine. 41 g of the polyoxypropylene diacrylate having a repeating unit number of 7 was placed in a dropping device, and it took 1 hour to drip. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 12 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (5) of the present invention having a solid content of 100%. The antifoaming agent (5) had a number average molecular weight of 1,354 and a weight average molecular weight of 1,393. Further, the fluorine content was 35.9 mass%.

According to the analysis by NMR, the antifoaming agent (5) is an average of 2.0 moles of polyoxypropylene diacrylate in a molar unit of 7 moles of 3, 3, 4, 4, 5, 5, 6 a compound of 6,7,7,8,8,8-tridecafluorooctanethiol.

Example 6 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 36 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 1 g of triethylamine. 14 g of the polyoxyethylene diacrylate having the repeating unit number of 4 was attached to a dropping device, and it took 1 hour to drip. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 12 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (6) of the present invention having a solid content of 100%. The antifoaming agent (6) had a number average molecular weight of 1,157 and a weight average molecular weight of 1,165. Further, the fluorine content was 46.2% by mass.

According to the analysis by NMR, the defoaming agent (6) is an average of 2.0 moles of polyoxyethylene diacrylate in a molar unit of 1 mole of 3, 3, 4, 4, 5, 5, 6 a compound of 6,7,7,8,8,8-tridecafluorooctanethiol.

Example 7 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 35 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 1 g of triethylamine. 15 g of the polyoxybutylene diacrylate having a repeating unit number of 4 was attached to a dropping device, and it took 1 hour to drip. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 12 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (7) of the present invention having a solid content of 100%. The antifoaming agent (7) had a number average molecular weight of 1,283 and a weight average molecular weight of 1,306. Further, the fluorine content was 44.9 mass%.

According to the analysis by NMR, the defoaming agent (7) is an average of 2.0 moles of polyoxybutylene diacrylate in a molar unit of 4 moles of 3, 3, 4, 4, 5, 5, A compound of 6,6,7,7,8,8,8-tridecafluorooctanethiol.

Example 8 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 38 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 1 g of triethylamine. 12g of repeating unit number 2 polyoxidation The propylene diacrylate was attached to a dropping device and it took 1 hour to drip. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 12 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (8) of the present invention having a solid content of 100%. The antifoaming agent (8) had a number average molecular weight of 1,080 and a weight average molecular weight of 1,084. Further, the fluorine content was 49.3% by mass.

According to the analysis by NMR, the defoaming agent (8) is an average of 2.0 moles of polyoxypropylene diacrylate in a molar unit of 2 moles of 3, 3, 4, 4, 5, 5, 6 a compound of 6,7,7,8,8,8-tridecafluorooctanethiol.

Example 9 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 97 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 3 g of triethylamine. It took 1 hour to drip 3 g of dipentaerythritol hexaacrylate. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 6 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (9) of the present invention having a solid content of 100%. The antifoaming agent (9) had a number average molecular weight of 3,022 and a weight average molecular weight of 3,107. Further, the fluorine content was 51.8% by mass.

According to the analysis by NMR, the antifoaming agent (9) is added to the average of 5.7 moles of 1,3-molar 3,3,4,4,5,5,6,6,7,7 in 1 mole of dipentaerythritol hexaacrylate. a compound of 8,8,8-tridecafluorooctanethiol.

Example 10 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 99 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 3 g of triethylamine. It takes 1 hour to drip 1g of dipentaerythritol. Hexaacrylate. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 6 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (10) of the present invention having a solid content of 100%. The antifoaming agent (10) had a number average molecular weight of 3,022 and a weight average molecular weight of 3,107. Further, the fluorine content was 51.8% by mass.

According to the analysis by NMR, the defoamer (10) is added to the average of 5.7 moles of 1,3-molar 3,3,4,4,5,5,6,6,7,7 in 1 mole of dipentaerythritol hexaacrylate. a compound of 8,8,8-tridecafluorooctanethiol.

Example 11 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 39 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 1 g of triethylamine. 11 g of 1,6-hexanediol diacrylate was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 6 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (11) of the present invention having a solid content of 100%. The antifoaming agent (11) had a number average molecular weight of 978 and a weight average molecular weight of 982. Further, the fluorine content was 50.1% by mass.

According to the analysis by NMR, the antifoaming agent (11) was added to a molar of 1,6-hexanediol diacrylate in an amount of 2.0, 3, 3, 4, 4, 5, 5, 6 a compound of 6,7,7,8,8,8-tridecafluorooctanethiol.

Example 12 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 37 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 1 g of triethylamine. It took 13 hours to drip 13 g of 1,10-decanediol diacrylate. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 6 hours. in After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (12) of the present invention having a solid content of 100%. The antifoaming agent (12) had a number average molecular weight of 1,119 and a weight average molecular weight of 1,123. Further, the fluorine content was 47.4% by mass.

According to the analysis by NMR, the antifoaming agent (12) was added to a molar of 1,10-decanediol diacrylate in an amount of 2.0 moles of 3,3,4,4,5,5,6. a compound of 6,7,7,8,8,8-tridecafluorooctanethiol.

Example 13 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 36 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 1 g of triethylamine. It took 1 hour to drip 14 g of tricyclodecane dimethanol diacrylate. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 6 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain an antifoaming agent (13) of the present invention having a solid content of 100%. The antifoaming agent (13) had a number average molecular weight of 988 and a weight average molecular weight of 992. Further, the fluorine content was 46.4% by mass.

According to the analysis by NMR, the antifoaming agent (13) was added to a molar of 1,10-decanediol diacrylate in an amount of 2.0 moles of 3,3,4,4,5,5,6. a compound of 6,7,7,8,8,8-tridecafluorooctanethiol.

Example 14 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 29 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 1 g of triethylamine. 21 g of 9,9-bis[4-(2-propenyloxyethoxy)phenyl]indole was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 6 hours. After the reaction is terminated, it is not reversed by distillation under reduced pressure. The antifoaming agent (14) of the present invention having a solid content of 100% was obtained from the raw material. The antifoaming agent (14) had a number average molecular weight of 1,256 and a weight average molecular weight of 1,261. Further, the fluorine content was 37.8% by mass.

According to the analysis by NMR, the antifoaming agent (14) is an average of 2.0 moles of 1 molar 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene. , 3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanethiol compound.

Example 15 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 38.5 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-13 was added to the air stream. Fluorooctanethiol and 1 g of triethylamine. It took 1 hour to drip 11.5 g of dipentaerythritol hexaacrylate. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 6 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a defoaming agent (15) of the present invention having a solid content of 100%. The antifoaming agent (15) had a number average molecular weight of 2,759 and a weight average molecular weight of 2,861. Further, the fluorine content was 50.1% by mass.

According to the analysis by NMR, the antifoaming agent (15) is added to the average of 4.7 moles of 1,3-molar 3,3,4,4,5,5,6,6,7,7 in 1 mole of dipentaerythritol hexaacrylate. a compound of 8,8,8-tridecafluorooctanethiol.

Comparative Example 1 (Comparative control antifoaming agent)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 25 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 1 g of triethylamine. 26 g of the polyoxypropylene acrylate having a repeating unit number of 6 was attached to a dropping device, and it took 1 hour to drip. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 12 hours. After the reaction is over, by The unreacted raw material was distilled off under reduced pressure to obtain a comparative antifoaming agent (1') having a solid content of 100%. The antifoaming agent (1') had a number average molecular weight of 1,126 and a weight average molecular weight of 1,205. Further, the fluorine content was 30.9% by mass.

According to the analysis by NMR, the comparative defoaming agent (1') was compared with an average of 1.0 moles of polyoxypropylene acrylate of 1 mole of repeating unit number of 6, 3, 4, 4, 5, A compound of 5,6,6,7,7,8,8,8-tridecafluorooctanethiol.

Comparative Example 2 (ibid.)

In a glass flask equipped with a stirring device, a condenser and a thermometer, 20 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorofluoride was added to the air stream. Octanethiol and 0.1 g of triethylamine. 30 g of dipentaerythritol hexaacrylate was placed in a dropping device, and it took 1 hour to drip. After the completion of the dropwise addition, the mixture was stirred at 85 ° C for 12 hours. After the completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain a comparative antifoaming agent (2') having a solid content of 100%. The antifoaming agent (2') had a number average molecular weight of 1,157 and a weight average molecular weight of 1,165. Further, the fluorine content was 25.8% by mass.

According to the analysis by NMR, the comparative antifoaming agent (2') was added to the average of 1.8 moles of 1,2,4,4,5,5,6,6 in 1 mole of pentaerythritol hexaacrylate. a compound of 7,7,8,8,8-tridecafluorooctanethiol.

Comparative Example 3 (ibid.)

In a glass flask equipped with a stirring device and a thermometer, 4 g of 1,3-propanediamine and 51 g of toluene were added, and the mixture was stirred at 5 °C. 46 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorooctyl chlorosulfonyl group was dissolved in 102 g of toluene and installed in a dropping device. Drip in 2 hours. After the end of the drop Stir at 5 ° C for 2 hours. After the completion of the reaction, 50 g of ion-exchanged water and 50 g of n-butanol were added and stirred for 1 hour. The solid obtained by vacuum filtration was dried by vacuum filtration to obtain a comparative antifoaming agent (3') having a solid content of 100%. The antifoaming agent (3') had a number average molecular weight of 968 and a weight average molecular weight of 967. Further, the fluorine content was 55.2% by mass.

Test Examples 1 to 16 and Comparative Test Examples 1 to 7

The solvent solution containing the obtained antifoaming agent and a fluorine-based surfactant was prepared by blending as shown in Table 1, and the defoaming property of the solvent solution was evaluated. The preparation method and evaluation method of the solvent solution are shown below. The results of this evaluation are shown in Table 1.

<Evaluation method of defoaming property>

The content of the antifoaming agent in terms of mass conversion is 0.1%, and the content of the fluorine-based surfactant in terms of mass conversion is 1.0%. To propylene glycol monomethyl ether acetate (hereinafter, abbreviated as PGMEA), a solvent solution was obtained. 50 g of this solvent solution was added to a 100 ml glass bottle and sealed, and the glass bottle was placed in a constant temperature layer at 25 ° C for 30 minutes. Then, by vibrating the glass bottle 10 times with a width of 20 cm, bubbles were generated on the liquid surface of the solvent solution. Immediately after the generation of the bubble, the glass bottle was allowed to stand, and the time (T0) until the liquid level of the solvent solution was started due to the disappearance of the bubble was measured as the starting point. The shorter the time is, the more the surfactant of the solvent solution which is excellent in defoaming property is obtained.

Table 1 footnote

Fluorine-based surfactant (1): Megaface F-554 manufactured by DIC Corporation

Fluorine-based surfactant (2): Megaface F-560 manufactured by DIC Corporation

Fluorine-based surfactant (3): Megaface F-561 manufactured by DIC Corporation

Antifoaming agent (4'): Non-polyoxygenated polymer type defoamer (BYK-1790) manufactured by BYK-Chemie Japan Co., Ltd.

Example 17 [Coating composition (photoresist composition) of the present invention]

27 parts by weight of a condensate of 2,3,4-trihydroxydiphenyl ketone and o-naphthyloxydiazido-5-sulfonylsulfonyl group, and 100 parts by mass of condensed cresol and formaldehyde The phenolic resin is dissolved in 400 parts by weight of propylene glycol methyl ether acetate, and the solution is adjusted so that the content of the antifoaming agent (1) by mass conversion is 0.05%, and The fluorine-based surfactant (F-554) was blended in the solution in such a manner that the content ratio by mass conversion was 0.5%, and a mixed solution was obtained. The mixed solution was precisely filtered with a filter made of polytetrafluoroethylene having a pore size of 0.2 μm to obtain a coating composition (1) [photoresist composition (1)] of the present invention.

The coating composition (1) [photoresist composition (1)] was spin-coated on a chromium vapor-deposited glass substrate having a 10 cm angle on one side at a rotation of 500 rpm to form a coating composition on the glass substrate (1) [The coating film of the photoresist composition (1)]. Then, the glass substrate on which the coating film was formed was allowed to stand in an environment of 110 ° C for 1 minute to dry the coating film.

With respect to the dried coating film, the occurrence of defects (contraction, uneven particles) on the coated surface was visually observed by using a sodium lamp, and the surface smoothness of the coating film was evaluated by the following criteria.

○: On the surface of the coating film, almost no shrinkage or uneven particles were observed.

△: On the surface of the coating film, partial shrinkage and uneven particles were observed.

×: Many shrinkage and uneven particles were observed on the surface of the coating film.

Examples 17 to 31 and Comparative Examples 4 to 10

The coating composition (2) [photoresist composition (2)] to the coating composition (15) of the present invention was obtained in the same manner as in Example 11 except that the antifoaming agent and the surfactant shown in Table 2 were used. Photoresist composition (15)] and comparative control coating composition (comparative control photoresist composition) (1') to (7'). The smoothness of the surface of the coating film was evaluated in the same manner as in Example 11. The results are shown in Table 2.

Claims (9)

An antifoaming agent characterized by having (meth) propylene fluorenyl compound (a1) in one molecule of 1 mole, and Michael addition 2~k molar having fluorine The alkyl group is reacted with the active hydrogen compound (a2), wherein k is 2 or more. The antifoaming agent of claim 1, wherein the k is 2 to 40. The antifoaming agent according to claim 1, wherein the compound (a2) having a fluorinated alkyl group and an active hydrogen is a compound represented by the following formula (1) or a compound represented by the following formula (2): Rf(CH ₂ ) _m ZH (1) where m is an integer from 0 to 20; Rf is -C _n F _2n+1 , where n is an integer from 1 to 20; Z is an alkane having a carbon number of 1 to 24. a nitrogen atom, an oxygen atom, a sulfur atom or -SO ₂ -NR-, wherein R is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms of; Wherein Y is an oxygen atom or a sulfur atom; p and q are each an integer from 1 to 4; Rf and Rf ¹ are each -C _n F _2n+1 , and n is an integer from 1 to 20; L and L ¹ are respectively A carbonyl group, an alkyl group having a carbonyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. The antifoaming agent according to claim 3, wherein the Z-based hydrogen atom in the formula (1) or a nitrogen atom having a carbon number of 1 to 6 or a sulfur atom or -SO ₂ -NR-, wherein R is carbon A number of 1 to 6 alkyl groups. The antifoaming agent according to claim 1, wherein the compound (a1) having k (meth) acrylonitrile groups in one molecule is selected from the group consisting of compounds represented by the following formula (3) (a1-1) a compound (a1-2) represented by the following formula (5), a urethane (meth) acrylate (a1-3), a tris(meth) acrylate containing a cyanurate ring One or more compounds selected from the group consisting of (a1-4) and tris(meth)acrylate (a1-5); wherein k is 2 or more, In the formula, R' is an alkyl group having 1 to 24 carbon atoms, an alkylcarbonyloxy group having 1 to 24 carbon atoms, CH ₂ =CHCO ₂ CH ₂ -, and CH ₂ =C(CH ₃ )CO ₂ CH ₂ - a (poly)oxyalkylene group, an alkylol group having 1 to 12 carbon atoms, and a carboxyl group, which are blocked by a repeating number of 1 or more and having a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Or a group represented by the following formula (4), R ¹ is a (meth) acrylonitrile group, R ² is a hydrogen atom or an alkylcarbonyl group having 1 to 18 carbon atoms, r is 2 or 3, and s is 0. Or 1 and r+s=3; In the formula, R ³ is a (meth) acrylonitrile group, and R ⁴ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl ester group having 1 to 18 carbon atoms or a carboxyl group, and t is an integer of 0 to 3. , u is an integer from 0 to 3 and t+u=3; R ⁷ OL-OR ⁶ (5) wherein R ⁶ and R ⁷ are respectively (meth)acryl fluorenyl groups, and L is a carbon number of 1 to 18 The alkyl group, the repeating unit number is 1 to 30, the alkylene group having 1 to 4 carbon atoms, the cyclic hydrocarbon group having 3 to 100 carbon atoms or the aromatic hydrocarbon group having 6 to 100 carbon atoms. The antifoaming agent according to claim 5, wherein the compound (a1) having k (meth) acrylonitrile groups in one molecule is a compound represented by the formula (3), or has two or more ( a urethane (meth) acrylate obtained by reacting a methyl group-containing hydroxy group-containing hydroxy group-containing (meth) acrylate (x1) with an isocyanate compound (x2), wherein, in the formula (3), R' is a linear alkyl group having 1 to 4 carbon atoms, CH ₂ =CHCO ₂ CH ₂ -, CH ₂ =C(CH ₃ )CO ₂ CH ₂ - or an alkylol group having 1 to 3 carbon atoms, or It is a group represented by the above formula (4), and R ³ is a hydrogen atom or an alkylcarbonyl group having 1 to 12 carbon atoms, wherein k is 2 or more. A surfactant composition comprising the antifoaming agent according to any one of claims 1 to 6 and a fluorine-based surfactant. A coating composition comprising the antifoaming agent according to any one of claims 1 to 6 and a fluorine-based surfactant. A photoresist composition comprising the antifoaming agent according to any one of claims 1 to 6 and a fluorine-based surfactant.