JP4346530B2 - Fluorine-containing polymerizable monomer and fluorine-containing polymer compound - Google Patents

Description

  The present invention relates to a novel fluorine-containing polymerizable monomer, a fluorine-containing polymer compound, and a photosensitive resin composition using the same.

  In recent years, with the development of digital devices such as computers, the processing amount of processing data, 2D and 3D image data has become enormous, and a large-capacity and high-speed memory is required to quickly process such information. And a high performance microprocessor is needed. In addition, with the development of networks such as the Internet, it is predicted that the use of broadband will accelerate further and the processing capability required for digital devices will increase further.

  In order to achieve such a demand, various devices, substrates, or modules represented by semiconductors are required to have higher density and higher integration. In particular, the demand for photolithographic technology that enables microfabrication and photosensitive patterning technology as a heat-resistant material required for packaging materials has become stricter year by year. Especially in the advanced semiconductor field, the minimum line width is 0.13 microns or less. Processing technology is required, and recently, development has been progressing in the region of 0.09 microns or less.

In response to such development or device production, photolithography using a KrF excimer laser (248 nm) and an ArF excimer laser (193 nm) has begun to be used. Further, for the purpose of processing a fine pattern, development of photolithography using F ₂ (157 nm), an electron beam, a soft X-ray, or the like is also in progress. More recently, development of immersion lithography that develops water and other fluids on a resist film and irradiates light through the fluid has also been activated.

  In these wavelength regions, a photosensitive material transparent to the wavelength of the active energy ray to be used is used. For example, hydroxystyrene-based polymers are used for KrF (248 nm), but acrylic resins (for example, Patent Document 1) and cycloolefin-based resins (for example, Patent Document 2) have been studied for ArF (193 nm). ing.

Furthermore, at a wavelength of F ₂ (157 nm), the superiority of fluororesins has become clear because highly transparent resins are limited. In particular, it has been reported that a resist resin containing a fluorine-based hydroxyl group has excellent properties in hydrophilicity, and is very promising (for example, Non-Patent Documents 1 and 2).

On the other hand, epoxy resin is generally used in the field of semiconductor devices and display packages, but elements are included in the sealing resin material for the purpose of reducing thermal stress during mounting on printed circuit boards. A method of adding fine particles of silicon oxide (SiO ₂ ) having a thermal expansion coefficient close to that of a substrate (Si substrate) is used. However, in the conventional technology, a plastic package having a conventional structure using an epoxy resin that is inferior to metal or ceramics in terms of thermal conductivity has poor heat dissipation characteristics and considerably high thermal resistance. It is disadvantageous in terms of long-term reliability as a package of high power consumption IC or IC that operates at high speed.

    In addition, the SiO2 fine particles added to the resin to reduce the stress are very hard, so the thermal stress generated during mounting on the printed circuit board applies a large pressure to the element surface to destroy the element. It was happening. That is, in the field of semiconductor packages, a material that has high heat resistance and is difficult to apply thermal stress to the element surface has been demanded (for example, Patent Document 3).

  Actually, it is difficult to satisfy the required performance with a single semiconductor package material, and various protective films are used in combination. It can be said that the package material and the protective film play a role by making up for each other's drawbacks. A passivation film is used to prevent water and impurities from entering the semiconductor chip, and a buffer coat film is used to alleviate stress concentration generated in the package material. Conventionally, inorganic compounds such as silicon oxide have been the mainstream for thin film materials such as insulating films and protective films used in semiconductors, but now the availability of heat-resistant polymer materials such as polyimide has been recognized, and correlation insulating films It is used for passivation film, buffer coating film, etc.

  Further, in response to the recent demand for higher integration and higher speed of semiconductors, materials corresponding to high-speed signal transmission are required. In high-speed transmission, signal propagation delay becomes a problem, but since the propagation delay is proportional to the relative dielectric constant of the material, it is effective to reduce the dielectric constant of the material. At present, fluororesins are known to have a low dielectric constant, and fluorine-containing polyimides are also being studied as one of the promising materials.

Resin into which fluorine atoms have been introduced has unique properties such as water repellency and non-adhesive properties of fluorine, and it can sometimes be used for the intended purpose. Sometimes it was difficult. With the advent of new semiconductor application products in recent years, semiconductor packages have also been diversified, and various demands such as downsizing, thinning, and low dielectric constant have been made, and package materials that satisfy these requirements have been desired.
JP-A-10-161313 JP 2000-89463 A JP-A-8-241913 H. Ito, HD Truong, et al, J. Photopolym. Sci. Technol., 16, 523-536 (2003) Francis Houlihan, Andrew Romano, Ralph R, Dammel, et al, J. Photopolym. Sci. Technol., 16, 581-590 (2003)

  It has high transparency in a wide wavelength range from the ultraviolet region to the near infrared region, and has high adhesion to the substrate and film formability, heat resistance, solvent resistance, dielectric properties, mechanical stability, and Provided are novel fluorine-containing polymerizable monomers and fluorine-containing polymer compounds useful for resist materials and photosensitive materials having high etching resistance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a novel acrylic amide compound having hexafluoroisopropanol and amide at the ortho position of the aromatic ring. Furthermore, it discovered that an acrylamide type polymer compound could be manufactured using this compound.

That is, the present invention
"1" General formula (1)

Is a fluorine-containing polymerizable monomer represented by the formula: (In the formula, R1 is hydrogen, a hydrocarbon group that may contain fluorine having 1 to 4 carbon atoms, chlorine, or a cyano group, and R2 is hydrogen, a methyl group, or a branch having 1 to 10 carbon atoms, A hydrocarbon group which may have a cyclic structure, or an alkoxy group, which may contain fluorine in part, and R3 is hydrogen or a protective group, which has an ether structure, an ester structure, fluorine. May be included.)
"2" General formula (2) using a polymerizable monomer of the above general formula (1)

It is a fluorine-containing high molecular compound containing the structure represented by these. (In the formula, R ¹ is hydrogen, a hydrocarbon group which may contain fluorine having 1 to 4 carbon atoms, fluorine, chlorine, cyano group, and R ² is hydrogen, fluorine, hydroxy group, methyl group, or A hydrocarbon group which may have a branched or cyclic structure having 1 to 10 carbon atoms, or an alkoxy group, and may partially or entirely contain fluorine, R ³ is hydrogen or a protecting group. And may contain an ether structure, an ester structure, or fluorine.)
"3" General formula (3)

Is a fluorine-containing polymerizable monomer represented by the formula: (In the formula, R ¹ is hydrogen, a hydrocarbon group which may contain fluorine having 1 to 4 carbon atoms, fluorine, chlorine, cyano group, and R ² is hydrogen, fluorine, hydroxy group, methyl group, or A hydrocarbon group which may have a branched or cyclic structure having 1 to 10 carbon atoms, or an alkoxy group, which may partially or entirely contain fluorine.
"4" General formula (4)

A fluorine-containing polymer compound containing a structure represented by: (In the formula, R ¹ is hydrogen, a hydrocarbon group which may contain fluorine having 1 to 4 carbon atoms, fluorine, chlorine, cyano group, and R ² is hydrogen, fluorine, hydroxy group, methyl group, or A hydrocarbon group which may have a branched or cyclic structure having 1 to 10 carbon atoms, or an alkoxy group, which may partially or entirely contain fluorine.
“5” The polymerizable monomer represented by the general formula (1) is the polymerizable monomer described in the above “1” having the structure of the formula (5).

"6" Formula (6) using a polymerizable monomer of the above formula (5)

The fluorine-containing polymer compound according to the above “2”, which contains a structure represented by the formula:
“7” The polymerizable monomer represented by the general formula (3) is 4,4-bis (trifluoromethyl) -2-isopropenyl-6-methyl-3,1-benzoxazine represented by the formula (7). The polymerizable monomer as described in “3” above.

“8” The polymer compound according to “4”, wherein the polymer compound represented by the general formula (4) is represented by the formula (8).

  Below, the synthesis | combining method of the following monomer shown by Formula (5) as a typical example of General formula (1) of this invention is demonstrated.

  The synthesis of this monomer, 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -phenyl] -2-propenamide, It consists of the following two steps.

  First step: A step of producing 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol represented by the following formula (9) by reacting 4-toluidine and hexafluoroacetone.

  Second step: 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol obtained in the first step and amidation using methacrylic acid halide or methacrylic anhydride, and the formula ( 5) 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -phenyl] -2-propenamide represented by 5) is obtained. Process.

  First, the first step will be described in detail. In this step, 4-toluidine and hexafluoroacetone are reacted to produce 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol. This step is performed by introducing hexafluoroacetone into 4-toluidine as a raw material. Since the boiling point of hexafluoroacetone is low (−28 ° C.), it is preferable to use a device (cooling device or sealed reactor) for preventing the hexafluoroacetone from flowing out of the reaction system. A vessel is particularly preferred.

  The amount of hexafluoroacetone used in this step is preferably 0.9 equivalents to 1.5 equivalents, more preferably 1.0 equivalents to 1.2 equivalents, relative to 4-toluidine. Although the reaction proceeds without problems even if it is used more than this, it is not preferable from the viewpoint of economy.

  This step is usually performed at a reaction temperature of 40 ° C. or higher, which is the melting point of 4-toluidine, and at the melting point of the product 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol. It is preferable to carry out at a certain 110 degreeC or more, and 120 to 180 degreeC is especially preferable. A side reaction proceeds at a temperature of 180 ° C. or higher, which is not preferable.

  Although this step can be performed without using a catalyst, the reaction can be promoted by using an acid catalyst. Examples of the acid catalyst used include Lewis acids such as aluminum chloride and boron fluoride, benzenesulfonic acid, camphorsulfonic acid (CSA), p-toluenesulfonic acid (pTsOH), pyridinium p-toluenesulfonic acid (PPTS), and the like. Organic sulfonic acids are preferred. The amount of the catalyst used is preferably from 0.1 mol% to 10 mol%, particularly preferably from 0.5 mol% to 5 mol%, relative to 1 mol of 4-toluidine. Although the reaction proceeds without problems even if it is used more than this, it is not preferable from the viewpoint of economy.

  Although this step can be performed without using a solvent, a solvent can also be used. The solvent to be used is not particularly limited as long as it does not participate in the reaction, but aromatic hydrocarbons such as xylene are preferable. The amount of the solvent to be used is not particularly limited, but it is not preferable to use a large amount because the yield per volume decreases.

  When this process is carried out using a sealed reactor (autoclave), usually 4-toluidine and optionally a catalyst and / or solvent are initially charged in the reactor. Subsequently, it is preferable to introduce hexafluoroacetone successively while raising the temperature so that the internal pressure of the reactor does not exceed 0.5 MPa.

  Although there is no special restriction | limiting in the reaction time of this process, optimal reaction time changes with temperature, the quantity of the catalyst to be used, etc. Therefore, it is preferable to carry out the reaction while measuring the progress of the reaction by a general-purpose analysis means such as gas chromatography and confirm that the raw materials are sufficiently consumed, and then terminate this step. After completion of the reaction, 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol can be obtained by ordinary means such as extraction, distillation, and crystallization. If necessary, it can be purified by column chromatography or recrystallization.

  Next, the second step will be described in detail. This step uses 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol (formula (9)) obtained in the first step and methacrylic acid halide or methacrylic anhydride. Amidation and 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -phenyl] -2-propenamide (formula (5) ).

  Specific examples of the methacrylic acid halide or methacrylic acid anhydride used in this step include methacrylic acid fluoride, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide and methacrylic acid anhydride. Of these, it is preferable to use methacrylic acid chloride or methacrylic anhydride from the viewpoint of price and availability. The amount of methacrylic acid chloride or methacrylic anhydride to be used is 0.9 equivalent to 1.equivalent to 1 equivalent of 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol. 5 equivalent is preferable, More preferably, it is 1.0 equivalent-1.2 equivalent. If it is used more than this, a by-product is generated, which is not preferable.

  A base is used for the amidation in this step. The base used is sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, sodium hydride, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide. In addition, inorganic bases such as triethylamine, diethylamine, pyridine, 2,6-lutidine, piperidine, pyrrolidine, and 1,8-diazabicyclo [5,4,0] -7-undecene can be used. Preferably, an organic base is used, and pyridine or 2,6-lutidine is particularly preferably used. The base is used in an amount of 1.8 to 5 equivalents, preferably 2 to 3 equivalents, per equivalent of 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol. This step is usually performed in a temperature range of −78 ° C. to 50 ° C., preferably −10 ° C. to 40 ° C., particularly preferably 0 ° C. to 30 ° C. A temperature higher than 50 ° C. is not preferable because a by-product is generated.

  Although this step can be performed without using a solvent, a solvent can also be used. The solvent to be used is not particularly limited as long as it does not participate in the reaction, but aromatic hydrocarbons such as benzene, toluene and xylenes or diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane and the like. Ethers are preferred. Although there is no restriction | limiting in particular in the quantity of the solvent to be used, It is preferable to use 1-10 times weight with respect to 2-amino-5-methyl-alpha, alpha-bis (trifluoromethyl) -benzenemethanol, The weight is preferably 2 to 5 times. There is no problem even if it is used in a large amount, but it is not preferable because the yield per volume is reduced.

  Although there is no special restriction | limiting in the reaction time of this process, optimal reaction time differs depending on temperature etc. Therefore, it is preferable to carry out the reaction while measuring the progress of the reaction by a general-purpose analysis means such as gas chromatography and confirm that the raw materials are sufficiently consumed, and then terminate this step. After completion of the reaction, 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-is obtained by usual means such as extraction and crystallization. Phenyl] -2-propenamide can be obtained. If necessary, it can be purified by column chromatography or recrystallization.

  If the polymerizable monomer of the general formula (1) that can be used in the present invention is specifically exemplified,

However, it is not limited to these. For example, the following acid labile group that can be dissociated by the action of an acid can be suitably used as R ₃ in the general formula (1).

That is, examples of the acid labile group that can be used for R ₃ can be used without limitation as long as they are groups that undergo elimination due to effects such as a photoacid generator or hydrolysis. For example, an alkoxycarbonyl group, an acetal group, a silyl group, an acyl group, and the like can be given.

  Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group, a tert-amyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and an i-propoxycarbonyl group.

  As an acetal group, methoxymethyl group, ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group, ethoxybutyl group, An ethoxyisobutyl group etc. are mentioned. An acetal group in which vinyl ether is added to a hydroxyl group can also be used.

  Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, and t-butyl. Examples thereof include a dimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

  As the acyl group, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauryl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, Glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioroyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canholoyl group, benzoyl group, phthaloyl group Group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonicotinoyl group And the like can be given.

  Further, those in which some or all of the hydrogen atoms of these acid labile groups are substituted with fluorine atoms can also be used.

  The purpose of using an acid labile group is to develop solubility in an alkaline aqueous solution after exposure to high energy rays such as ultraviolet rays, vacuum ultraviolet rays, excimer lasers, X-rays, or electron beams. Those having a fluorine atom in the functional group provide transparency, and those having a cyclic structure further impart characteristics such as etching resistance and a high glass transition point, and can be selectively used for each application field of the present invention.

The polymer compound that can be used in the present invention is represented by the general formula (2).

If it contains the structure (wherein R ₁ , R ₂ and R ₃ are as described above), they can be used without limitation. For example, the polymerizable monomer of the general formula (1) can be homopolymerized or copolymerized with any polymerizable monomer as shown below.

  Examples of the polymerizable monomer that can be copolymerized include olefin, maleic anhydride, acrylic ester, fluorine-containing acrylic ester, methacrylic ester, fluorine-containing methacrylate, styrene compound, fluorine-containing styrene compound, vinyl ether, Copolymerization with one or more monomers selected from fluorine-containing vinyl ethers, vinyl esters, fluorine-containing vinyl esters, allyl ethers, fluorine-containing allyl ethers, olefins, fluorine-containing olefins, norbornene compounds, fluorine-containing norbornene compounds, and vinyl silanes. Is preferred.

  Examples of the olefin include ethylene and propylene, and examples of the fluoroolefin include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, hexafluoroisobutene, and octafluorocyclopentene. .

  Moreover, as an acrylic ester or methacrylic ester, it can use without a restriction | limiting especially about an ester side chain. Examples of known compounds are methyl acrylate or methacrylate, ethyl acrylate or methacrylate, n-propyl acrylate or methacrylate, isopropyl acrylate or methacrylate, n-butyl acrylate or methacrylate, isobutyl acrylate or methacrylate, n-hexyl acrylate or methacrylate. , N-octyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, lauryl acrylate or methacrylate, 2-hydroxyethyl acrylate or methacrylate, alkyl ester of acrylic acid or methacrylic acid such as 2-hydroxypropyl acrylate or methacrylate, ethylene glycol, propylene Glycol, tetramethylene glycol Acrylates or methacrylates containing an alkyl group, further unsaturated amides such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, diacetone acrylamide, vinyl silane or acrylic acid containing acrylonitrile, methacrylonitrile, alkoxysilane, or Methacrylic acid ester, t-butyl acrylate or methacrylate, 3-oxocyclohexyl acrylate or methacrylate, adamantyl acrylate or methacrylate, alkyladamantyl acrylate or methacrylate, cyclopentyl or cyclohexyl acrylate or methacrylate, cyclopentyl or cyclohexyl having one or two hydroxyl groups Acrylate or methacrylate, hydroxyl Adamantyl acrylate or methacrylate having one or two, tricyclodecanyl acrylate or methacrylate, butyl lactone, acrylate or methacrylate having a special lactone ring having a norbornane ring and a lactone ring at the same time, norbornane ring is directly or indirectly An acrylate or methacrylate esterified, acrylic acid, methacrylic acid or the like can be used. The above-mentioned various cyclic acrylates or methacrylates may be any of primary, secondary and tertiary esters. Furthermore, acrylate, methacrylate, norbornene, styrene, or the like having a structure having one or more hexafluorocarbinol groups in the side chain can also be used. Further, various acrylates, methacrylates, norbornenes and styrenes having sulfonic acid, carboxylic acid, hydroxyl group, and cyano group in the side chain can also be used. Furthermore, maleic acid, fumaric acid, maleic anhydride and the like can be copolymerized as the above acrylate compounds containing α cyano group or similar compounds.

  In the present invention, as a copolymer system suitably employed, in addition to a combination with acrylic acid ester, methacrylic acid ester and styrene, acrylic acid amide having a fluoroalkyl group introduced at the alpha position of general formula (1) and Copolymerization of norbornene monomers is also a suitable combination.

  The polymerization method of the polymer compound according to the present invention is not particularly limited as long as it is a generally used method, but radical polymerization, ionic polymerization and the like are preferable, and in some cases, coordination anion polymerization, living anion polymerization, cation Polymerization or the like can be used.

  Radical polymerization is carried out in the presence of a radical polymerization initiator or a radical initiator by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, and is either batch-wise, semi-continuous or continuous. This can be done by operation.

  The radical polymerization initiator is not particularly limited, and examples thereof include azo compounds, peroxide compounds, and redox compounds. Particularly, azobisisobutyronitrile, t-butylperoxypivalate, Di-t-butyl peroxide, i-butyryl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnamyl peroxide, di-n-propyl peroxydicarbonate, t-butyl peroxyallyl monocarbonate, benzoyl peroxide, Hydrogen peroxide, ammonium persulfate and the like are preferable.

  The reaction vessel used for the polymerization reaction is not particularly limited. In the polymerization reaction, a polymerization solvent may be used. As the polymerization solvent, it is sufficient that the polymerization reaction is not hindered. Representative examples include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, hydrocarbons such as hexane, heptane and cyclohexane, acetone, Halogenation of ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and t-butanol, carbon tetrachloride, chloroform, methylene chloride and 1,2-dichloroethane Examples include hydrocarbons, water, ethers, cyclic ethers, and chlorofluorocarbons. These solvents can be used alone or in admixture of two or more. The reaction temperature is usually preferably -70 to 200 ° C, particularly preferably -30 to 60 ° C.

  According to this invention, it can be set as the photosensitive resin composition using the high molecular compound containing General formula (2). Since the hexafluoroisopropanol group is an acidic hydroxyl group, it utilizes the fact that it functions as a soluble group in an alkaline developer. In the general formula (2), a method of copolymerizing with a polar group-containing monomer is selected for specific purposes such as enhancing alkali solubility and enhancing adhesion. As an example, in order to improve the solubility of the polymer compound of the general formula (2) in an alkaline aqueous solution such as a developer, acrylic acid, methacrylic acid, and these carboxyl groups may be substituted with alkyladamantane or t-butyl group. Copolymerization with a monomer protected with a typical acid labile group, and further with a monomer containing a hexafluoroalcohol group shown below is also preferably employed.

X is 1 or 2
According to the present invention, it is possible to impart photosensitivity by accompanying a chemical reaction with irradiation of active energy rays. The method is not particularly limited, but a compound whose solubility is changed by the action of an acid, such as a naphthoquinone diazide compound or other acid labile compound, and a method in which a polymer is mixed with a solubility inhibitor (inhibitor) is also an example. .

On the other hand, an acid labile group that can be dissociated by the action of an acid can be used as R ₃ in the general formula (2). In this case, the polymer having the general formula (2) itself can be made positive photosensitive. That is, the hexafluoroisopropanol group in the molecule is protected with an acid labile protecting group, then mixed with a photoacid generator to form a resist, and this is exposed to light to release the acid labile group, producing a hexafluoropropanol group. As a result, alkali development becomes possible.
That is, the fluorine-containing polymer compound of the present invention is effective in any type of resist material such as a positive type, a negative type, and a chemical amplification type, and can be used by changing its blending amount and blending method for each application. is there.

  The polymer compound of the present invention can be applied to the resist field. As a method of using the resist material, it is possible to use a resist pattern forming method of a conventional photoresist technique. That is, a resist material solution is first applied to a substrate such as a silicon wafer using a spinner and dried to form a photosensitive layer, and high energy rays are passed through a desired mask pattern by an exposure apparatus or the like. Irradiate and heat. Next, this is developed using a developer, for example, an alkaline aqueous solution such as a 0.1 to 10% by weight tetramethylammonium hydroxide aqueous solution. With this forming method, a pattern faithful to the mask pattern can be obtained. Further, additives that are miscible with the resist material as desired, such as additional resins, quenchers, plasticizers, stabilizers, colorants, surfactants, thickeners, leveling agents, antifoaming agents, compatibilizing agents, Various additives such as an adhesive and an antioxidant can be contained.

When the polymer compound of the present invention is used in the resist field, it can be processed by irradiation with high energy rays. The high energy beam to be used is not particularly limited, but particularly when performing microfabrication, high energy such as G2 ray, I ray, F2 excimer laser, ArF excimer laser, KrF excimer laser or soft X-ray is used. It is effective to use an exposure apparatus having a line source. In addition, using a medium that absorbs high energy rays, such as water or a fluorine-based solvent, in part of the optical path, and an immersion exposure system that enables more efficient microfabrication at the numerical aperture and effective wavelength Is possible.
The compound represented by the general formula (1) of the present invention can be converted into a monomer compound represented by the general formula (3) by cyclization.

  The cyclization reaction is not particularly limited, but the cyclization can be performed by various methods that promote dehydration conditions such as heat and an acid catalyst.

When cyclized, various physical properties are expected to change compared to non-cyclized monomers. When resin is used, physical properties are improved in heat resistance, solubility changes, refractive index and dielectric constant decrease. It is expected to exhibit low water absorption and water / oil repellency.
By polymerizing the monomer represented by the general formula (3), a polymer compound represented by the general formula (4) can be produced. The monomer of the general formula (3) can be homopolymerized or copolymerized. As the conditions for the polymerization reaction, the monomer conditions represented by the general formula (1) can be applied. That is, it is possible to perform polymerization under the same conditions as in the case of the general formula (1) with respect to the reaction conditions such as the reaction solvent, reaction temperature, type and amount of initiator, compound capable of copolymerization and the like.

Furthermore, by cyclizing the polymer of the general formula (2), the general formula (4)
It is also possible to use a polymer compound having the structure:

  The cyclization reaction is not particularly limited, but as in the case of the monomer, the cyclization can be performed by various methods that promote dehydration conditions such as heat and an acid catalyst.

  In the case of cyclization, it is possible to carry out resin modification accompanied by large changes in physical properties such as improvement in heat resistance, change in solubility, reduction in refractive index and dielectric constant, low water absorption, and expression of water and oil repellency.

  In addition, when cyclization is performed, the film can be strengthened by cyclization in a state of being patterned as a photosensitive resin, and can be processed into a semi-permanent pattern that is optically and electrically important.

  The fluorine-containing polymer compound represented by the present invention can be suitably used as an optical device material such as a resist material for semiconductor devices, a package material, and an optical waveguide. As a package material for a semiconductor device, a sealing material and an overcoat material are typical, and as an overcoat material, a buffer coat film, a passivation film, and a protective film thereof are typical. In particular, the fluorine-containing polymer compound represented by the general formula (4) of the present invention has a high heat resistance because it has a cyclic structure in the molecule, and also has good solvent solubility derived from a hexafluoroisopropanol structure and a coating property. Excellent in film formability and moldability, types of substituents contained in the molecule, types of monomers to be copolymerized, their composition, blending ratio with other materials to be mixed, curing agent It is possible to obtain physical properties suitable for each application depending on the type.

  Further, for the purpose of improving chemical, mechanical or electrical characteristics, it can be blended with a filler or other resin, and is preferably employed. As a method for packaging a semiconductor device, a known method can be used and is not particularly limited. For example, sealing by a transfer molding method, sealing by a potting method, spin coating method, roll coating method, dipping method, etc. There is a method for forming a thin film by.

  Hereinafter, the present invention will be described by way of examples.

[Example 1] Production of 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol (Formula 9) 21.46 g of 4-toluidine in a 100 ml glass sealed container (autoclave) 0.2 mol) and 1.00 g (5.8 mmol, 2.9 mol%) of pTsOH were charged, and the inside of the system was put into a nitrogen atmosphere. Subsequently, 21.04 g (0.13 mol, 0.65 equivalent) of hexafluoroacetone was introduced, and then the temperature was raised, and the internal temperature of the reaction solution was set to 120 ° C. Next, hexafluoroacetone was sequentially introduced for 2 hours, and finally, 36.52 g (0.22 mol, 1.1 equivalent) of hexafluoroacetone was introduced. Thereafter, the reaction solution was cooled, and 100 ml of diisopropyl ether and 100 ml of n-hexane were added. The mixture was heated and then cooled and recrystallized, and 40.2 g of the desired 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol (yield 73.5%, (Purity 98.8%).

Example 2 2-Methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -phenyl] -2-propenamide (formula ( 5)) Preparation In a 100 ml glass flask, 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol 6.65 g (24.3 mmol), pyridine 3.85 g (48.7 mmol, 2.0 equivalents) and 30 ml of toluene, and cooled to 5 ° C. in an ice bath. Then, 2.54 g (24.3 mmol, 1.0 equivalent) of methacrylic acid chloride was added dropwise over 5 minutes. When the ice bath was removed and the mixture was gradually warmed to room temperature, the reaction was completed after 3 hours. Subsequently, 40 ml of 1M dilute hydrochloric acid and 30 ml of diisopropyl ether were added for extraction, and the obtained organic layer was washed with saturated brine. The organic layer was then dried over magnesium sulfate and concentrated to give crude 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl). -Phenyl] -2-propenamide (8.19 g, yield 99%, purity 93.7%) was obtained. The obtained crude product was recrystallized from 30 ml of diisopropyl ether and 15 ml of n-heptane, and the desired 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2, 6.22 g (yield 75%, purity 98.0%) of 2-trifluoroethyl) -phenyl] -2-propenamide was obtained.

Properties of 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -phenyl] -2-propenamide White solid. Mp 132-134 ° C. ¹ H-NMR (reference material: TMS, solvent: CDCl ₃ ) σ (ppm): 1.94 (s, 3H), 2.30 (s, 3H), 5.37 (s, 1H), 5.83 (S, 1H), 6.65 (br, 1H), 7.02 (d, 1H, J = 8.2 Hz), 7.25 (s, 1H), 8.01 (d, 1H, J = 8) .2 Hz), 9.52 (br, 1H). ¹⁹ F-NMR (reference substance: CCl ₃ F, solvent: CDCl ₃ ) σ (ppm): −74.5 (s, 6F). Example 3 2-Methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -phenyl] -2-propenamide (formula ( 5)) Production Into a 1 l glass flask, 120 g (439 mmol) of 2-amino-5-methyl-α, α-bis (trifluoromethyl) -benzenemethanol, 69.5 g (879 mmol, 2.0 eq) of pyridine, 600 ml of diisopropyl ether was added and cooled to 5 ° C. in an ice bath. Then, 45.9 g (439 mmol, 1.0 equivalent) of methacrylic acid chloride was added dropwise over 50 minutes. When the ice bath was removed and the mixture was gradually warmed to room temperature, the reaction was completed after 2 hours. Next, the reaction solution was washed with 300 ml of 1M dilute hydrochloric acid and saturated brine. The organic layer was then dried over magnesium sulfate and concentrated to give crude 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl). 148 g (yield 99%, purity 89.9%) of -phenyl] -2-propenamide were obtained. The obtained crude product was recrystallized from 550 ml of diisopropyl ether and 250 ml of n-heptane, and the desired 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2, 115 g (yield 76%, purity 99.0%) of 2-trifluoroethyl) -phenyl] -2-propenamide were obtained.

Properties of 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -phenyl] -2-propenamide White solid. Mp 132-134 ° C. ¹ H-NMR (reference material: TMS, solvent: CDCl ₃ ) σ (ppm): 1.94 (s, 3H), 2.30 (s, 3H), 5.37 (s, 1H), 5.83 (S, 1H), 6.65 (br, 1H), 7.02 (d, 1H, J = 8.2 Hz), 7.25 (s, 1H), 8.01 (d, 1H, J = 8) .2 Hz), 9.52 (br, 1H). ¹⁹ F-NMR (reference substance: CCl ₃ F, solvent: CDCl ₃ ) σ (ppm): −74.5 (s, 6F). [Example 4] Production of 4,4-bis (trifluoromethyl) -2-isopropenyl-6-methyl-3,1-benzoxazine (formula (6)) Into a 50 ml glass flask was added 2-amino-5. -Methyl-α, α-bis (trifluoromethyl) -benzenemethanol 1.0 g (3.66 mmol) and toluene 5 ml were added, and the mixture was cooled to 5 ° C. in an ice bath. Then, 459 mmg (4.39 mmol, 1.2 equivalents) of methacrylic acid chloride was added dropwise. The ice bath was removed and the mixture was gradually warmed to room temperature. Seven hours later, 230 mg (2.20 mmol, 0.6 equivalent) of methacrylic acid chloride was added dropwise. After further stirring for 18 hours, 10 ml of 1M dilute hydrochloric acid was added, and the mixture was extracted with 15 ml of diisopropyl ether. The organic layer was washed with saturated brine. Thereafter, the organic layer was dried over magnesium sulfate and concentrated to obtain 1.23 g of crude 4,4-bis (trifluoromethyl) -2-isopropenyl-6-methyl-3,1-benzoxazine. The obtained crude product was purified by silica gel column chromatography, and 325 mg (yield 28%) of the desired 4,4-bis (trifluoromethyl) -2-isopropenyl-6-methyl-3,1-benzoxazine. , Purity 93.2%).

Physical properties of 4,4-bis (trifluoromethyl) -2-isopropenyl-6-methyl-3,1-benzoxazine Light yellow liquid. ¹ H-NMR (reference material: TMS, solvent: CDCl ₃ ) σ (ppm): 2.01 (s, 3H), 2.32 (s, 3H), 5.51 (s, 1H), 6.01 (S, 1H), 7.21 (m, 3H). ¹⁹ F-NMR (reference material: CCl ₃ F, solvent: CDCl ₃ ) σ (ppm): −76.7 (s, 6F).

  [Example 5] A flask equipped with a reflux condenser and a stirrer was charged with 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-) under a nitrogen stream. Trifluoroethyl) -phenyl] -2-propenamide (1.00 g), methyl ethyl ketone (2.00 g) and AIBN (19 mg) were added, heated in an oil bath at 75 ° C. and stirred for 14 hours.

  After completion of the reaction, the mixture was added to a mixed solvent (100 ml) of n-hexane and acetone 9: 1 and stirred, and the produced precipitate was filtered out. This was vacuum-dried at 50 ° C. for 3 hours to obtain a white solid polymer (0.97 g). The molecular weight was determined from gel permeation chromatography (GPC, standard polystyrene). The results are shown in Table 1.

  [Example 6] 2-Methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-) was added to a flask equipped with a reflux condenser and a stirrer under a nitrogen stream. (Trifluoroethyl) -phenyl] -2-propenamide (0.50 g), ethyl methacrylate (0.17 g), methyl ethyl ketone (1.30 g), AIBN (19 mg), heated in an oil bath at 75 ° C. and stirred for 14 hours did.

  After completion of the reaction, the mixture was added to a mixed solvent (100 ml) of n-hexane and acetone 9: 1 and stirred, and the produced precipitate was filtered out. This was vacuum-dried at 50 ° C. for 3 hours to obtain a white solid polymer (0.61 g). The molecular weight was determined from gel permeation chromatography (GPC, standard polystyrene). The results are shown in Table 1.

  Example 7 A flask equipped with a reflux condenser and a stirrer was charged with 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2-) under a nitrogen stream. (Trifluoroethyl) -phenyl] -2-propenamide (0.5 g), hydroxyethyl methacrylate (0.19 g), methyl ethyl ketone (1.4 g), AIBN (19 mg) were added and heated in an oil bath at 75 ° C. for 14 hours. Stir.

  After completion of the reaction, the mixture was added to a mixed solvent (100 ml) of n-hexane and acetone 9: 1 and stirred, and the produced precipitate was filtered out. This was vacuum-dried at 50 ° C. for 3 hours to obtain a white solid polymer (0.67 g). The molecular weight was determined from gel permeation chromatography (GPC, standard polystyrene). The results are shown in Table 1.

[Example 8] 4,4-bis (trifluoromethyl) -2-isopropenyl-6-methyl-3,1 synthesized in Example 4 in a flask equipped with a reflux condenser and a stirrer under a nitrogen stream -Benzoxazine (0.16 g), methyl ethyl ketone (1.00 g), and AIBN (25 mg) were added, heated in an oil bath at 75 ° C, and stirred for 14 hours.

  After completion of the reaction, the mixture was added to a mixed solvent (100 ml) of n-hexane and acetone 9: 1 and stirred, and the produced precipitate was filtered out. This was vacuum-dried at 50 ° C. for 3 hours to obtain a white solid polymer (0.07 g). The molecular weight was Mw = 7,400 as determined from gel permeation chromatography (GPC, standard polystyrene). When it was compression molded by thermoforming, a transparent film was obtained.

Since the fluorine-containing polymer compound of the present invention has good solvent solubility derived from the hexafluoroisopropanol structure, it has excellent coating properties, excellent film formability and moldability, and can be used for resist materials and photosensitive materials. Available.

Claims (8)

General formula (1)
A fluorine-containing polymerizable monomer represented by: (In the formula, R ¹ is hydrogen, a hydrocarbon group which may contain fluorine having 1 to 4 carbon atoms, fluorine, chlorine, cyano group, and R ² is hydrogen, fluorine, hydroxy group, methyl group, or A hydrocarbon group which may have a branched or cyclic structure having 1 to 10 carbon atoms, or an alkoxy group, and may partially or entirely contain fluorine, R ³ is hydrogen or a protecting group. And may contain an ether structure, an ester structure, or fluorine.) General formula (2) using the polymerizable monomer of the above general formula (1)
(Wherein, R ¹ is hydrogen, a hydrocarbon group that may contain fluorine having 1 to 4 carbon atoms, fluorine, chlorine, cyano group, R ² is hydrogen, fluorine, a hydroxy group, a methyl group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group which may have a cyclic structure, or an alkoxy group, which partially or entirely contains fluorine. R ³ is hydrogen or a protective group, and may contain an ether structure, an ester structure, or fluorine). General formula (3)
(Wherein, R ¹ is hydrogen, a hydrocarbon group that may contain fluorine having 1 to 4 carbon atoms, fluorine, chlorine, or a cyano group, and R ² is Hydrogen, fluorine, hydroxy group, methyl group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group which may have a cyclic structure, or an alkoxy group, which may partially or entirely contain fluorine. .) General formula (4)
(Wherein, R ¹ is hydrogen, a hydrocarbon group that may contain fluorine having 1 to 4 carbon atoms, fluorine, chlorine, cyano group, R ² is hydrogen, fluorine, a hydroxy group, a methyl group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group which may have a cyclic structure, or an alkoxy group, which partially or entirely contains fluorine. Is also good.) The polymerizable monomer represented by the general formula (1) is 2-methyl-N- [4-methyl-2- (1-hydroxy-1-trifluoromethyl-2,2,2) of the formula (5). 2. The polymerizable monomer according to claim 1, which is -trifluoroethyl) -phenyl] -2-propenamide.
Using the polymerizable monomer of the above formula (5), the formula (6)
The fluorine-containing high molecular compound of Claim 2 containing the structure represented by these. The polymerizable monomer represented by the general formula (3) is 4,4-bis (trifluoromethyl) -2-isopropenyl-6-methyl-3,1-benzoxazine of the formula (7) Item 4. The polymerizable monomer according to Item 3.
The polymer compound according to claim 4, wherein the polymer compound represented by the general formula (4) is represented by the formula (8).