WO2014017236A1 - ラジカル硬化性化合物、ラジカル硬化性化合物の製造方法、ラジカル硬化性組成物、その硬化物、及びレジスト材料用組成物 - Google Patents
ラジカル硬化性化合物、ラジカル硬化性化合物の製造方法、ラジカル硬化性組成物、その硬化物、及びレジスト材料用組成物 Download PDFInfo
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- AAAQKTZKLRYKHR-UHFFFAOYSA-N c1ccc(C(c2ccccc2)c2ccccc2)cc1 Chemical compound c1ccc(C(c2ccccc2)c2ccccc2)cc1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
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- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
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- C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
- C07C37/002—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain by transformation of a functional group, e.g. oxo, carboxyl
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- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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- C07C67/00—Preparation of carboxylic acid esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/10—Esters
- C08F22/12—Esters of phenols or saturated alcohols
- C08F22/14—Esters having no free carboxylic acid groups
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Definitions
- the present invention relates to a radical curable compound that gives a cured product having excellent heat resistance.
- the nanoimprint method is attracting attention as a technique for ultra fine patterning with a line width of 20 nm or less.
- This nanoimprint method is roughly classified into a thermal nanoimprint method and an optical nanoimprint method.
- the thermal nanoimprint method heats above the glass transition temperature, presses the mold onto a softened polymer resin, releases the mold after cooling, and transfers the microstructure to the resin on the substrate, making the nanopattern relatively inexpensive It is expected to be applied to various fields.
- the thermal nanoimprint method since it is necessary to soften the polymer resin by heating, it is difficult to use a polymer resin having a high crow transition temperature, and in recent years, the application to the electric and electronic fields where higher heat resistance is required. Application was difficult.
- the photo-curable resin applied to photo-nanoimprint includes radical polymerization type and ion polymerization type, and hybrid type of these, and any type of curable composition can be used for nanoimprint applications.
- radical polymerization type photocurable compositions have been widely studied.
- the nanoimprint material When used as a thin film transistor for liquid crystal displays, a protective film for liquid crystal color filters, a spacer, or a permanent film for microfabrication of other liquid crystal display device components, it has high mechanical properties for cured products of nanoimprint materials. Transparency, light resistance, heat resistance and the like are required, and particularly high heat resistance is required.
- a material from which a cured product having high heat resistance can be obtained for example, epoxy (meth) acrylate resin having a biphenyl skeleton is known (for example, refer to Patent Document 1). Did not have.
- the problem to be solved by the present invention is to provide a radical curable compound that gives a cured product excellent in heat resistance, and further to provide a method for producing the compound.
- a cured product obtained by curing a compound having a structure obtained by reacting a trifunctional phenol having a specific structure with (meth) acrylic acid halide has a very high heat resistance. It has been found that the compound can be easily produced by such a method, and the present invention has been completed.
- R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 8 carbon atoms, m and n are each independently an integer of 1 to 4, and p is 0 to 4
- X, Y, and Z are each independently an acryloyloxy group, a methacryloyloxy group, or a hydroxyl group, and at least one of X, Y, and Z is an acryloyloxy group or a meta An acryloyloxy group, and t is 1 or 2.
- the present invention provides the following general formula (3) by polycondensation of an alkyl-substituted phenol (a1) and an aromatic aldehyde (a2) having a hydroxyl group on the benzene ring.
- R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 8 carbon atoms, m and n are each independently an integer of 1 to 4, and p is 0 to 4 is an integer, and s is 1 or 2.
- this invention provides the radical curable compound obtained by the said manufacturing method.
- the present invention provides a radical curable composition containing the radical curable compound.
- the present invention provides a cured product obtained by curing the radical curable composition with active energy rays or heat.
- the present invention provides a composition for a resist material comprising the radical curable composition.
- the radical curable compound of the present invention can provide a cured product having a very high level of heat resistance. Therefore, the radically curable compound of the present invention can be used as a material for solder resist and a material for nanoimprint, which require high heat resistance. Moreover, since the radically curable compound of the present invention is a material that has photocurability and is capable of stereolithography, it can also be used as a template material for the thermal nanoimprint method.
- a thermoplastic resin used for a resist in the thermal nanoimprint method when an engineering plastic for electrical / electronic materials having a glass transition temperature (Tg) exceeding 200 ° C. such as polyphenylene ether (PPE) having high heat resistance is used.
- Tg glass transition temperature
- PPE polyphenylene ether
- the softening temperature of the plastic is 300 ° C. or higher, but the cured product of the radical curable compound of the present invention has very high heat resistance and can be used as a mold material.
- the radical curable compound of the present invention since the radical curable compound of the present invention has a high density of benzene rings, it becomes a more rigid skeleton, and the cured product has high heat resistance. Furthermore, due to its rigid skeleton, the cured product also has high mechanical properties (impact resistance), high water resistance, especially high hardness. Therefore, the radical curable compound of the present invention is used for films such as triacetyl cellulose (TAC) used for polarizing plates of liquid crystal displays such as televisions, video cameras, computers, mobile phones and the like that require high surface hardness.
- TAC triacetyl cellulose
- Hard coat material Hard coat material for transparent protective film for protecting the surface of various displays such as liquid crystal display, plasma display, organic EL display, etc .
- the radical curable compound of this invention can be easily manufactured with the manufacturing method of this invention.
- FIG. 1 is a chart of the 1 H-NMR spectrum of the radical curable compound (1) obtained in Example 1.
- FIG. 1 is a chart of the 1 H-NMR spectrum of the radical curable compound (1) obtained in Example 1.
- the radical curable compound of the present invention has the following general formula (1)
- R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 8 carbon atoms, m and n are each independently an integer of 1 to 4, and p is 0 to 4
- X, Y, and Z are each independently an acryloyloxy group, a methacryloyloxy group, or a hydroxyl group, and at least one of X, Y, and Z is an acryloyloxy group or a meta An acryloyloxy group, and t is 1 or 2.
- R 1 , R 2 and R 3 in the general formula (1) are each independently an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include n-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.
- These alkyl groups impart high heat resistance to the cured product.
- R 1 , R 2 and R 3 are all preferably methyl groups.
- m and n are each independently an integer of 1 to 4, and p is an integer of 0 to 4.
- an integer of 1 to 3 is more preferable for reasons such as high reactivity, ease of reaction design, and availability of industrial raw materials.
- X, Y and Z in the general formula (1) are each independently any of an acryloyloxy group, a methacryloyloxy group or a hydroxyl group.
- t in general formula (1) is 2, two Z which exists in a molecule
- numerator may be the same, and may mutually differ.
- At least one of X, Y, and Z is an acryloyloxy group or a methacryloyloxy group, and more preferably, since all of X, Y, and Z are acryloyloxy groups or a compound having excellent curability, It is preferably a methacryloyloxy group.
- X, Y, and Z are acryloyloxy groups, it becomes a radically curable compound that provides a cured product with a high curing rate and high adhesion to the substrate.
- X, Y, and Z are methacryloyloxy groups, a radically curable compound is obtained that has a cured shrinkage and a cured product with high adhesion to the substrate.
- T in the general formula (1) is an integer of 1 or 2, and t is preferably 1 from the viewpoint of easy availability of industrial raw materials and ease of reaction design.
- the bonding position of X and Y in the general formula (1) is preferably in the para position with respect to the methine group linking three aromatic rings because a cured product having high heat resistance is obtained. Accordingly, more preferable embodiments of the radical curable compound represented by the general formula (1) are respectively represented by the following general formula (2).
- radical curable compound represented by the general formula (1) include those having a molecular structure represented by any of the following structural formulas (1-1) to (1-14).
- the radical curable compound of the present invention is obtained by, for example, polycondensing an alkyl-substituted phenol (a1) and an aromatic aldehyde (a2) having a hydroxyl group on a benzene ring, thereby obtaining the following general formula (3)
- R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 8 carbon atoms, m and n are each independently an integer of 1 to 4, and p is 0 to 4 is an integer, and s is 1 or 2.
- (meth) acrylic acid means one or both of “acrylic acid” and “methacrylic acid”.
- the alkyl-substituted phenol (a1) is a compound in which part or all of the hydrogen atoms bonded to the aromatic ring of the phenol are substituted with an alkyl group.
- this alkyl group has 1 carbon atom such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.
- an alkyl group of ⁇ 8, and a methyl group is particularly preferable.
- alkyl-substituted phenol (a1) examples include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, pt-butylphenol, o Monoalkylphenols such as cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol; dialkyl such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol, 2,6-xylenol Examples include alkylphenols; trialkylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol.
- alkyl-substituted phenols those having 2 substitutions of alkyl groups on the aromatic ring of the phenol are preferred because of their excellent heat resistance, and 2,5-xylenol and 2,6-xylenol are particularly preferred.
- These alkyl-substituted phenols (a1) can be used alone or in combination of two or more.
- the aromatic aldehyde having a hydroxyl group on the benzene ring (a2) is, for example, hydroxybenzaldehyde such as 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde; 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde Dihydroxybenzaldehydes such as 2-hydroxy-4-methylbenzaldehyde, 2-hydroxy-5-methylbenzaldehyde, 2-hydroxy-3,5-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde and the like containing hydroxy groups Examples include benzaldehyde.
- aromatic aldehydes hydroxybenzaldehyde is preferred because of its industrial availability, and excellent balance between heat resistance and alkali solubility. Among them, 4-hydroxybenzaldehyde, 4-hydroxy-3,5- Dimethylbenzaldehyde is more preferred.
- aromatic aldehydes (a2) can be used alone or in combination of two or more.
- Examples of the halide of the (meth) acrylic acid halide (B) include fluorine, chlorine, bromine, iodine, and astatine.
- Specific examples of the (meth) acrylic acid halide include (meth) acrylic acid chloride, (meth) acrylic acid bromide, (meth) acrylic acid iodide, and the like.
- (meth) acrylic acid chloride is preferable because of its high reactivity and easy availability.
- Step 3 The polycondensate (A) isolated in Step 2 is reacted with the (meth) acrylic acid halide (B) in the presence of a base.
- Examples of the acid catalyst used in Step 1 include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts can be used alone or in combination of two or more. Of these acid catalysts, sulfuric acid and paratoluenesulfonic acid are preferred because of their excellent activity.
- the acid catalyst may be added before the reaction or during the reaction.
- the reaction temperature for polycondensing the alkyl-substituted phenol (a1) and the aromatic aldehyde (a2) having a hydroxyl group on the benzene ring is, for example, 60 to 140 ° C.
- the reaction time is, for example, 0.5 to 100 hours.
- the charge ratio [(a1) / (a2)] of the alkyl-substituted phenol (a1) and the aromatic aldehyde (a2) having a hydroxyl group on the benzene ring in the step 1 makes it easy to remove the unreacted alkyl-substituted phenol.
- a molar ratio of 1 / 0.2 to 1 / 0.5 is preferable, and 1 / 0.25 to 1 / 0.0. A range of 45 is more preferred.
- Examples of the polycondensate (A) obtained as a result of the polycondensation in Step 1 include compounds represented by the following general formulas (3-1) to (3-10).
- the polycondensate (A) is further recovered from the recovered product recovered from the reaction solution in step 2 to increase the purity of the polycondensate (A) as much as possible.
- the purity of the polycondensate (A) to be reacted with the (meth) acryloyl halide (B) is preferably 85% or more, more preferably 90% or more, still more preferably 94% or more, particularly preferably 98% or more. % Is most preferred.
- the purity of the polycondensate (A) can be determined from the area ratio in a chart of gel permeation chromatography (GPC).
- GPC measurement conditions are as follows.
- the crystallinity of the obtained radical curable compound of the present invention is increased. . Therefore, the radically curable compound of the present invention is easily packed finely.
- the radical curable compound of the present invention is cured while being packed finely. As a result, the molecular motion of the cured product is suppressed, and the glass transition temperature is 400 ° C. or higher, and the heat resistance twice as high as that of the conventional one can be expressed.
- Examples of the method for recovering the polycondensate (A) from the reaction solution in the step 2 include a precipitate obtained by adding the reaction solution to a poor solvent (S1) in which the reaction product is insoluble or hardly soluble.
- the reaction product is dissolved in a solvent (S2) that is mixed with the poor solvent (S1), and again added to the poor solvent (S1), and the resulting precipitate is filtered off. It is done.
- Examples of the poor solvent (S1) used in this case include water; monoalcohols such as methanol, ethanol, and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohyxane; toluene, xylene And aromatic hydrocarbons.
- water and methanol are preferable because the acid catalyst can be efficiently removed at the same time.
- examples of the solvent (S2) include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5- Polyols such as pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin; 2-ethoxyethanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether Glycol ethers such as ethylene glycol ethyl methyl ether and ethylene glycol mono
- Examples of the base used in Step 3 include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; tertiary amines such as triethylamine and trimethylamine; Examples include pyridine.
- alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
- alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate
- tertiary amines such as triethylamine and trimethylamine
- Examples include pyridine.
- potassium carbonate and tertiary amine are preferable because they can be easily removed from the reaction system after the reaction between the polycondensate (A) and the (meth) acrylic acid halide (B).
- potassium carbonate and triethylamine are preferred. Is more preferable.
- a solvent may be used as necessary.
- the solvent include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Polyols such as hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol Glycol ethers such as ruethyl methyl ether,
- solvents can be used alone or in combination of two or more.
- tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone are preferred because the resulting compound has excellent solubility.
- the reaction temperature for reacting the polycondensate (A) with the (meth) acrylic acid halide (B) is, for example, 20 to 80 ° C.
- the reaction time is, for example, 1 to 30 hours.
- the charge ratio of the polycondensate (A) and the (meth) acrylic acid halide (B) in Step 3 is that the radical curable compound of the present invention is obtained with high purity and good yield, so that the polycondensate (
- [(A ′) / (B)] is preferably in a range of 1/1 to 1/3 in terms of molar ratio, and 1/1 to 1 / A range of 2.5 is more preferred.
- the radical curable composition of the present invention contains the radical curable compound of the present invention as an essential component, and the radical curable compound of the present invention may be used alone or other radical curing. May contain a functional compound.
- radical curable compounds used herein include various epoxy (meth) acrylates and other (meth) acrylate compounds.
- Examples of the epoxy (meth) acrylate include those obtained by adding (meth) acrylic acid or a halide thereof to various polyglycidyl ether compounds.
- Examples of the various polyglycidyl ethers include hydroquinone, 2-methylhydroquinone, 1,4-benzenedimethanol, 3,3′-biphenol, 4,4′-biphenol, tetramethylbiphenol, biphenyl-3,3′-.
- Polyglycidyl ether of an aromatic ring-containing polyester polyol obtained by reacting an aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid or pimelic acid with the aromatic polyol;
- Aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid and their anhydrides, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1 Aliphatic polyols such as 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, trimethylolethane, trimethylolpropane, glycerin, etc.
- a polyglycidyl ether of an aromatic ring-containing polyester polyol obtained by reacting with an aliphatic polyol of
- Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin;
- novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins. These may be used alone or in combination of two or more.
- Examples of the other (meth) acrylate compounds include n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, glycidyl (meth) acrylate, morpholine ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (Meth) acryl
- the content of the radical curable compound of the present invention in the radical curable composition may be in a range where the effect of the present invention excellent in heat resistance in the cured product is not impaired.
- the radical curable compound of the present invention is used alone or in a total of 100 parts by mass of the radical curable compound of the present invention and other radical curable compounds, The amount is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more.
- the radical curable composition of the present invention can be made into a cured product by further adding a polymerization initiator and irradiating with active energy rays or applying heat to cure.
- radical curable composition of the present invention When the radical curable composition of the present invention is irradiated with active energy rays and cured by radical polymerization, an intramolecular cleavage type photopolymerization initiator or a hydrogen abstraction type photopolymerization initiator is used as the polymerization initiator.
- Examples of the intramolecular cleavage type photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4 -Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thio Acetophenone compounds such as methylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 4,6-trimethylbenzoindiphenyl Acylphosphine oxide compounds such as sphin oxide and bis (2,4,6-trimethylbenzoyl) -
- photopolymerization initiators 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl- An acetophenone compound such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone and benzophenone are preferred, and 1-hydroxycyclohexyl phenyl ketone is particularly preferred. These photopolymerization initiators can be used alone or in combination of two or more.
- the amount of the photopolymerization initiator used is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15% by weight, and more preferably 0.5 to 10 parts by weight based on 100 parts by weight of the radical curable composition of the present invention. Part by mass is more preferable.
- a photoinitiator is unnecessary.
- Examples of active energy rays used for curing the radical curable composition of the present invention include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- Examples of energy sources or curing devices that generate these active energy rays include germicidal lamps, ultraviolet lamps (black lights), carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, Examples thereof include an electrode lamp, a metal halide lamp, an ArF excimer laser, an ultraviolet LED, an ultraviolet ray using natural light as a light source, or an electron beam by a scanning type or curtain type electron beam accelerator.
- thermal radical polymerization initiator when the radical curable composition of the present invention is cured by thermal radical polymerization, a thermal radical polymerization initiator is used.
- the thermal radical polymerization initiator include benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 3,3,5-trimethylhexanoyl peroxide, di-2-ethylhexyl peroxydicarbonate, and methyl ethyl ketone.
- Peroxide t-butyl peroxyphthalate, t-butyl peroxybenzoate, di-t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-hexanoate, t-butyl peroxy -Organic peroxides such as 3,3,5-trimethylhexanoate; 1,1'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, 2-cyano-2-propylazoformamide And azo compounds.
- thermal radical polymerization initiators benzoyl peroxide and 1,1'-azobisisobutyronitrile are preferable.
- these thermal radical polymerization initiators can be used alone or in combination of two or more.
- the amount of the thermal radical polymerization initiator used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15% by mass, and more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the radical curable composition of the present invention. 10 parts by mass is more preferable.
- the measuring method of the NMR spectrum used for the identification of a compound is as follows.
- the obtained product was filtered and dried under vacuum to obtain a heavy polymer having a molecular structure represented by the following formula (5-1). 5.93 g of condensate (A-1) was obtained.
- the purity of the polycondensate (A-1) in the crude product is 87% by mass in terms of the area ratio of GPC, and the purity of the finally obtained polycondensate (A-1) is 99% by mass. there were.
- Test Examples 1 and 2 and Comparative Test Examples 1 to 6 Using the acrylates obtained in Example 1 and Comparative Synthesis Examples 1 to 3, cured products were prepared as shown in Test Examples 1 and 2 and Comparative Test Examples 1 to 6. According to the following method, the glass transition temperature of the cured product is measured and the heat resistance of the cured product is evaluated, and the results are shown in Table 1.
- Example 1 In place of the radical curable compound (1) used in Example 2, the same operation as in Example 2 was performed except that the BPA type epoxy acrylate obtained in Comparative Synthesis Example 1 was used to cure the BPA type epoxy acrylate. 0.23 g of product was obtained. The heat resistance (Tg) was evaluated in the same manner as in Test Example 1.
- Example 2 In place of the radical curable compound (1) used in Example 3, the same operation as in Example 3 was performed except that the BPA type epoxy acrylate obtained in Comparative Synthesis Example 1 was used to cure the BPA type epoxy acrylate. 0.13 g of product was obtained. The heat resistance (Tg) was evaluated in the same manner as in Test Example 1.
- Tg is 300 ° C. or higher.
- A: Tg is 250 ° C. or higher and lower than 300 ° C.
- Table 1 summarizes the raw materials, Tg values, and heat resistance evaluation results of the cured products obtained in Examples 2 to 3 and Comparative Examples 1 to 6 before curing.
- “> 400” of Tg in Examples 2 and 3 indicates that the glass transition point is not exhibited at a temperature higher than 400 ° C. and thermal decomposition occurs.
- Example 1 From the results shown in Table 1, the cured product of the radical curable compound of the present invention obtained in Example 1 (test examples 1 and 2) does not exhibit a glass transition point at a temperature higher than 400 ° C. From the decomposition, it was found that it has very good heat resistance.
- the cured products of epoxy acrylates of Comparative Examples 1 to 6 that had been considered to have high heat resistance had a Tg of 158 to 229 ° C., which was higher in heat resistance than the cured products of the radical curable compounds of the present invention. It turned out to be inferior.
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Abstract
Description
で表されることを特徴とするラジカル硬化性化合物を提供するものである。
で表される重縮合物(A)を得た後、該重縮合物に(メタ)アクリル酸ハライド(B)とを反応させることを特徴とするラジカル硬化性化合物の製造方法を提供するものである。
で表される分子構造を有する。
で表されるラジカル硬化性化合物となる。
で表される重縮合物(A)を得た後、該重縮合物に(メタ)アクリル酸ハライド(B)とを反応させる方法により容易に製造することができる。なお、本発明において、「(メタ)アクリル酸」とは、「アクリル酸」と「メタクリル酸」の一方又は両方をいう。
アルキル置換フェノール(a1)とベンゼン環上に水酸基を有する芳香族アルデヒド(a2)とを酸触媒存在下で重縮合することにより、反応溶液中に上記一般式(5)または一般式(6)で表される重縮合物(A)を含む粗生成物を得る。
工程1で得られた重縮合物(A)を反応溶液中から回収する。
工程2で単離した重縮合物(A)と(メタ)アクリル酸ハライド(B)とを塩基存在下で反応させる。
測定装置:東ソー株式会社製「HLC-8220 GPC」
カラム:昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)
+昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)
+昭和電工株式会社製「Shodex KF803」(8.0mmФ×300mm)
+昭和電工株式会社製「Shodex KF804」(8.0mmФ×300mm)
カラム温度:40℃
検出器: RI(示差屈折計)
データ処理:東ソー株式会社製「GPC-8020モデルIIバージョン4.30」
展開溶媒:テトラヒドロフラン
流速:1.0ml/分
試料:樹脂固形分換算で0.5質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの
注入量:0.1ml
標準試料:下記単分散ポリスチレン
東ソー株式会社製「A-500」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
日本電子株式会社製「JNM-GSX500(500MHz,DMSO-d6,TMS)」を用いて構造解析を行った。
冷却管を設置した100ml2口フラスコに2,5-キシレノール7.32g(60mmol)、4-ヒドロキシベンズアルデヒド2.44g(20mmol)を仕込み、2-エトキシエタノール20mlに溶解させた。氷浴中で冷却しながら硫酸2mlを添加した後、100℃のオイルバス中で2時間加熱、攪拌し反応させた。反応後、得られた溶液を水で再沈殿操作を行い粗生成物を得た。粗生成物をアセトンに再溶解し、さらに水で再沈殿操作を行った後、得られた生成物を濾別、真空乾燥を行い下記式(5-1)で表される分子構造を有する重縮合物(A-1)5.93gを得た。ここで、粗生成物における重縮合物(A-1)の純度はGPCの面積比で87質量%であり、最終的に得られた重縮合物(A-1)の純度は99質量%であった。
冷却管を設置した100ml2口フラスコに重縮合物(A-1)1.74g(5mmol)、炭酸カリウム4.10g(30mmol)、テトラヒドロフラン10mlを仕込み撹拌を開始した。氷浴中で冷却しながらアクリル酸クロライド3.60g(20mmol)を30分で滴下しながら添加した後、70℃のオイルバス中で12時間加熱、攪拌し反応させた。反応後、得られた溶液から固形分を濾別し、濾液をクロロホルム30mlと混合し、水50mlで3回洗浄を行った。下層である有機層を分取後、硫酸ナトリウムで乾燥した後、溶剤を減圧留去し白色針状結晶のラジカル硬化性化合物(1)1.79gを得た。1H-NMRの各ピークにより同定し、下記構造式(3-1)で表される化合物が100%の純度で得られたことを確認した。1H-NMRスペクトルのチャート図を図1に示す。
[1H-NMRスペクトル]
(ppm、500MHz、溶媒:DMSO-d6、基準:TMS)
1.9-2.2(12H;Ar-CH 3 ),5.6-5.8(1H;Ar-CH),6.1-6.3(3H;C-CH 2 ),6.4-6.5(3H;CO-CH-C),6.5-6.6(2H;Ar),6.6-6.7(3H;C-CH 2 ),6.9-7.3(6H;Ar)
ビスフェノールA(BPA)型液状エポキシ樹脂(DIC株式会社製「EPICLON850」;エポキシ当量188g/eq.)188質量部とアクリル酸72質量%(エポキシ基の数:総カルボキシル基の数=1:1となる比率)とを95℃で反応させて、透明粘調液体のBPA型エポキシアクリレート253質量部を得た。
テトラメチルビフェニル型液状エポキシ樹脂(三菱化学株式会社製「JER YX-4000H」;エポキシ当量195g/eq.)195質量部とアクリル酸72質量部(エポキシ基の数:総カルボキシル基の数=1:1となる比率)とを95℃で反応させて、透明粘調液体のテトラメチルビフェニル型エポキシアクリレート264質量部を得た。
o-クレゾールノボラック型エポキシ樹脂(DIC株式会社製「EPICLON N-695」;エポキシ当量214g/eq.)214質量部とアクリル酸72質量部(エポキシ基の数:総カルボキシル基の数=1:1となる比率)を100℃で反応させて、黄色固形のクレゾールノボラック型エポキシアクリレート273質量部を得た。
上記の実施例1及び比較合成例1~3で得られたアクリレートを用いて、試験例1、2及び比較試験例1~6に示すように硬化物を調製した。下記方法に従って、硬化物のガラス転移点温度の測定を行うと共に、硬化物の耐熱性の評価を行い、その結果を第1表に示す。
実施例1で得られたラジカル硬化性化合物(1)0.50gと、イルガキュア184〔チバ・スペシャリティ(株)製〕0.05gとテトラヒドロフラン0.5gをシュレンク管に入れ、窒素雰囲気下で凍結乾燥を行った。この反応器を密閉し、340nmのバンドパスフィルターを装着した高圧水銀灯で3時間光を照射した。得られた内容物をメタノールで再沈殿操作を行い、得られた沈殿物を濾過、真空乾燥を行い重合体(a)0.35gを得た。得られた重合体(a)のDSC測定を行い、耐熱性(Tg)を評価した。
実施例1で得られたラジカル硬化性化合物(1)0.50gと、アゾビスイソブチロニトリル〔AIBN;和光純薬(株)試薬〕0.05gとジクロロエタン0.5gをシュレンク管に入れ、窒素雰囲気下で凍結乾燥を行った。この反応器を密閉し、70℃で12時間反応を行った。得られた内容物をメタノールで再沈殿操作を行い、得られた沈殿物を濾過、真空乾燥を行い重合体(b)0.21gを得た。得られた重合体(b)のDSC測定を行い、耐熱性(Tg)を評価した。
実施例2で用いたラジカル硬化性化合物(1)に代えて、比較合成例1で得られたBPA型エポキシアクリレートを用いた以外は実施例2と同様の操作を行い、BPA型エポキシアクリレートの硬化物0.23gを得た。試験例1と同様にして耐熱性(Tg)を評価した。
実施例3で用いたラジカル硬化性化合物(1)に代えて、比較合成例1で得られたBPA型エポキシアクリレートを用いた以外は実施例3と同様の操作を行い、BPA型エポキシアクリレートの硬化物0.13gを得た。試験例1と同様にして耐熱性(Tg)を評価した。
実施例2で用いたラジカル硬化性化合物(1)に代えて、比較合成例2で得られたテトラメチルビフェニル型エポキシアクリレートを用いた以外は実施例2と同様の操作を行い、テトラメチルビフェニル型エポキシアクリレートの硬化物0.35gを得た。試験例1と同様にして耐熱性(Tg)を評価した。
実施例3で用いたラジカル硬化性化合物(1)に代えて、比較合成例2で得られたテトラメチルビフェニル型エポキシアクリレートを用いた以外は実施例3と同様の操作を行い、テトラメチルビフェニル型エポキシアクリレートの硬化物0.33gを得た。試験例1と同様にして耐熱性(Tg)を評価した。
実施例2で用いたラジカル硬化性化合物(1)に代えて、比較合成例3で得られたクレゾールノボラック型エポキシアクリレートを用いた以外は実施例2と同様の操作を行い、クレゾールノボラック型エポキシアクリレートの硬化物0.37gを得た。試験例1と同様にして耐熱性(Tg)を評価した。
実施例3で用いたラジカル硬化性化合物(1)に代えて、比較合成例3で得られたクレゾールノボラック型エポキシアクリレートを用いた以外は実施例3と同様の操作を行い、クレゾールノボラック型エポキシアクリレートの硬化物0.42gを得た。試験例1と同様にして耐熱性(Tg)を評価した。
示差熱走査熱量計(株式会社ティー・エイ・インスツルメント製「示差熱走査熱量計(DSC)Q100」)を用いて、窒素雰囲気下、温度範囲25~450℃、昇温速度10℃/分の条件で、ガラス転移温度(以下、「Tg」と略記する。)を測定した。
上記の測定で得られたTgの温度から、下記の基準にしたがって耐熱性を評価した。
◎:Tgが300℃以上である。
○:Tgが250℃以上300℃未満である。
△:Tgが200℃以上250℃未満である。
×:Tgが200℃未満である。
Claims (12)
- 前記R1、R2およびR3が何れもメチル基である請求項1記載のラジカル硬化性化合物。
- 前記m、n及びpがそれぞれ独立して1~3の整数である請求項1記載のラジカル硬化性化合物。
- 前記アルキル置換フェノール(a1)が、2,5-キシレノールまたは2,6-キシレノールである請求項5記載のラジカル硬化性化合物の製造方法。
- 前記ベンゼン環上に水酸基を有する芳香族アルデヒド(a2)が4-ヒドロキシベンズアルデヒドである請求項5記載のラジカル硬化性化合物の製造方法。
- アルキル置換フェノール(a1)とベンゼン環上に水酸基を有する芳香族アルデヒド(a2)とを酸触媒存在下で重縮合することにより、反応溶液中に重縮合物(A)を含む粗生成物を得る工程1と、工程1で得られた重縮合物(A)を反応溶液中から回収する工程2と、工程2で単離した重縮合物(A)と(メタ)アクリル酸ハライド(B)とを塩基存在下で反応させる工程3を含む請求項5記載のラジカル硬化性化合物の製造方法。
- 請求項5~8の何れか一つに記載の製造方法により得られるラジカル硬化性化合物。
- 請求項1~4、又は請求項9の何れか一つに記載のラジカル硬化性化合物を含有するラジカル硬化性組成物。
- 請求項10記載のラジカル硬化性組成物を活性エネルギー線または熱により硬化させて得られる硬化物。
- 請求項10記載のラジカル硬化性組成物からなるレジスト材料用組成物。
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CN201380039314.6A CN104487412B (zh) | 2012-07-25 | 2013-06-25 | 自由基固化性化合物、自由基固化性化合物的制造方法、自由基固化性组合物、其固化物、以及抗蚀材料用组合物 |
EP13822504.0A EP2878591B1 (en) | 2012-07-25 | 2013-06-25 | Radically curable compound, method for producing radically curable compound, radically curable composition, cured product thereof, and composition for resist material |
KR1020147030333A KR101955951B1 (ko) | 2012-07-25 | 2013-06-25 | 라디칼 경화성 화합물, 라디칼 경화성 화합물의 제조 방법, 라디칼 경화성 조성물, 그 경화물, 및 레지스트 재료용 조성물 |
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US15/259,787 US9550723B2 (en) | 2012-07-25 | 2016-09-08 | Radically curable compound, method for producing radically curable compound, radically curable composition, cured product of the same, and resist-material composition |
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WO2015080141A1 (ja) * | 2013-11-28 | 2015-06-04 | Jnc株式会社 | 光硬化性インクジェットインク |
WO2015080142A1 (ja) * | 2013-11-28 | 2015-06-04 | Jnc株式会社 | 光硬化性インクジェットインク |
WO2016084495A1 (ja) * | 2014-11-25 | 2016-06-02 | Dic株式会社 | ノボラック型フェノール樹脂、その製造方法、感光性組成物、レジスト材料、及び塗膜 |
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WO2021246182A1 (ja) * | 2020-06-03 | 2021-12-09 | Dic株式会社 | 硬化性樹脂、硬化性樹脂組成物、及び、硬化物 |
JP7060181B1 (ja) * | 2020-06-03 | 2022-04-26 | Dic株式会社 | 硬化性樹脂、硬化性樹脂組成物、及び、硬化物 |
WO2023162519A1 (ja) * | 2022-02-28 | 2023-08-31 | キヤノン株式会社 | パターン形成方法、及び物品製造方法 |
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KR101955951B1 (ko) | 2019-03-08 |
US9469592B2 (en) | 2016-10-18 |
EP2878591A1 (en) | 2015-06-03 |
EP2878591B1 (en) | 2020-09-16 |
KR20150037733A (ko) | 2015-04-08 |
US20150166459A1 (en) | 2015-06-18 |
EP2878591A4 (en) | 2016-04-06 |
US20160376218A1 (en) | 2016-12-29 |
US9550723B2 (en) | 2017-01-24 |
TWI572623B (zh) | 2017-03-01 |
JP5454749B1 (ja) | 2014-03-26 |
JPWO2014017236A1 (ja) | 2016-07-07 |
TW201404788A (zh) | 2014-02-01 |
CN104487412A (zh) | 2015-04-01 |
CN104487412B (zh) | 2016-08-24 |
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