WO2012121195A1 - ラジカル硬化性化合物及びその硬化物、並びに該化合物の製造方法 - Google Patents
ラジカル硬化性化合物及びその硬化物、並びに該化合物の製造方法 Download PDFInfo
- Publication number
- WO2012121195A1 WO2012121195A1 PCT/JP2012/055523 JP2012055523W WO2012121195A1 WO 2012121195 A1 WO2012121195 A1 WO 2012121195A1 JP 2012055523 W JP2012055523 W JP 2012055523W WO 2012121195 A1 WO2012121195 A1 WO 2012121195A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- curable compound
- radical curable
- independently
- carbon atoms
- compound according
- Prior art date
Links
- 0 *C(c(cc1)ccc1OC(C(*)=C)=O)c(cc1)cc(CN=*)c1OC(C(O*)=C)=O Chemical compound *C(c(cc1)ccc1OC(C(*)=C)=O)c(cc1)cc(CN=*)c1OC(C(O*)=C)=O 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers 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
- C08F122/10—Esters
- C08F122/12—Esters of phenols or saturated alcohols
- C08F122/14—Esters having no free carboxylic acid groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
- C07C57/42—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- 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
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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. Application to the electronic field has been 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.
- the present inventors have obtained, for example, a polycondensate of an alkyl-substituted phenol and an aromatic aldehyde, and then reacting the polycondensate with a (meth) acrylic acid halide.
- a cured product obtained by curing a compound having a structure has very high heat resistance, and the compound can be easily produced by such a method, thereby completing the present invention.
- R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, and R 3 and R 4 are each independently a hydrogen atom or a methyl group.
- M and n are And each independently represents an integer of 1 to 4.
- X is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 8 carbon atoms.
- the present invention provides a cured product obtained by curing the radical curable compound with active energy rays or heat.
- the present invention is a radical curability characterized by reacting a polycondensate (A) of an alkyl-substituted phenol (a1) and an aromatic aldehyde (a2) with a (meth) acrylic acid halide (B).
- a method for producing a compound is provided.
- 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 an IR spectrum chart of the radically polymerizable compound (1) obtained in Example 1.
- FIG. 2 is a chart of 1 H-NMR spectrum of the radical polymerizable compound (1) obtained in Example 1.
- FIG. 3 is a chart of 13 C-NMR spectrum of the radical polymerizable compound (1) obtained in Example 1.
- the radical curable compound of the present invention has the following general formula (1)
- R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, and R 3 and R 4 are each independently a hydrogen atom or a methyl group.
- M and n are And each independently represents an integer of 1 to 4.
- X is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 8 carbon atoms.
- R 1 and R 2 in the general formula (1) are each independently an alkyl group having 1 to 8 carbon atoms. These alkyl groups impart high heat resistance to the cured product. Among these alkyl groups, high rigidity is given to the molecule by suppressing molecular motion, high heat resistance can be given to the cured product, electron donating property to the phenolic benzene nucleus can be given, and industrial availability is easy. Therefore, a methyl group is preferable.
- R 3 and R 4 each independently represent a hydrogen atom or a methyl group.
- R 3 and R 4 are hydrogen atoms, a high curing rate and high adhesion to the substrate can be obtained, and if they are methyl groups, low curing shrinkage, high water resistance, and high hardness can be obtained.
- n and n are each independently preferably an integer of 1 to 3.
- X in the general formula (1) include a benzene ring, a benzene ring substituted with an alkyl group having 1 to 8 carbon atoms, a naphthalene ring, and an alkyl group having 1 to 8 carbon atoms.
- the naphthalene ring substituted with is preferably exemplified because a cured product having excellent heat resistance is obtained.
- examples of the radical curable compound in which X is a benzene ring or a benzene ring substituted with an alkyl group having 1 to 8 carbon atoms include the following compounds.
- R 1 , R 2 and R 5 are each independently an alkyl group having 1 to 8 carbon atoms, and R 3 and R 4 are each independently a hydrogen atom or a methyl group. And n are each independently an integer of 1 to 4, and p is an integer of 1 to 5.
- examples of the radical curable compound in which X is a naphthalene ring or a naphthalene ring substituted with an alkyl group having 1 to 8 carbon atoms include the following compounds.
- R 1 , R 2 , R 6 and R 7 are each independently an alkyl group having 1 to 8 carbon atoms, and R 3 and R 4 are each independently a hydrogen atom or a methyl group.
- M and n are each independently an integer of 1 to 4, and q and r are an integer of 1 to 7 in total.
- radical polymerizable compound represented by the general formula (3-1) examples include compounds represented by the following general formula (3-1-1) and general formula (3-1-2). Can be mentioned.
- radical polymerizable compound represented by the general formula (3-2) examples include, for example, compounds represented by the following general formula (3-2-1) and general formula (3-2-2) Is mentioned.
- R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, and R 3 and R 4 are each independently a hydrogen atom or a methyl group. M and n are And each independently represents an integer of 1 to 4.
- R 1 , R 2 , R 6 and R 7 are each independently an alkyl group having 1 to 8 carbon atoms, and R 3 and R 4 are each independently a hydrogen atom or a methyl group.
- M and n are each independently an integer of 1 to 4, and q and r are an integer of 1 to 7 in total.
- radical curable compounds of the present invention has a structure substituted with an alkyl group having 1 to 8 carbon atoms as X in the general formula (1) because it becomes a radical curable compound having good solvent solubility.
- Radical curable compounds are preferred.
- the radical curable compound of the present invention is, for example, a reaction of a polycondensate (A) of an alkyl-substituted phenol (a1) and an aromatic aldehyde (a2) with a (meth) acrylic acid halide (B).
- (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.
- the alkyl group include alkyl groups having 1 to 8 carbon atoms, 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 (a2) is a compound having at least one aldehyde group in the aromatic ring. Further, by using an aromatic aldehyde having an aromatic ring substituted with an alkyl group having 1 to 8 carbon atoms as the aromatic aldehyde (a2), a radical curable compound having more excellent solvent solubility, specifically, For example, a radical curable compound represented by the general formula (2-2), general formula (3-2), general formula (3-2-1), or general formula (3-2-2) is obtained. Can do.
- aromatic aldehyde (a2) examples include benzaldehyde; hydroxybenzaldehyde such as salicylaldehyde, m-hydroxybenzaldehyde, and p-hydroxybenzaldehyde; dihydroxybenzaldehyde such as 2,4-dihydroxybenzaldehyde and 3,4-dihydroxybenzaldehyde; p -Alkylbenzaldehydes such as tolualdehyde and cuminaldehyde; alkoxybenzaldehydes such as anisaldehyde and 3,4-dimethoxybenzaldehyde; vanillin compounds such as vanillin, orthovanillin, isovanillin and ethylvanillin; phthalaldehydes such as terephthalaldehyde and isophthalaldehyde; 1-naphthaldehyde, naphthaldehyde such as 2-naphthaldehyde; 2-hydroxy-1-na
- aromatic aldehydes one or more aldehydes selected from the group consisting of benzaldehyde, hydroxybenzaldehyde and naphthaldehyde are preferred because they are easily available industrially and have a good balance between heat resistance and alkali solubility. .
- 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.
- a polycondensate may be obtained in the presence of a solvent, if 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
- the reaction temperature for polycondensing the alkyl-substituted phenol (a1) and the aromatic aldehyde (a2) is, for example, 60 to 140 ° C.
- the reaction time is, for example, 0.5 to 100 hours.
- the charge ratio [(a1) / (a2)] between the alkyl-substituted phenol (a1) and the aromatic aldehyde (a2) in the step 1 is that the unreacted alkyl-substituted phenol can be easily removed, and the yield of the product And a high purity product is obtained, the molar ratio is preferably in the range of 1 / 0.2 to 1 / 0.5, more preferably in the range of 1 / 0.25 to 1 / 0.45.
- Examples of the polycondensate (A) obtained as a result of the polycondensation in the step 1 include compounds represented by the following general formula (4).
- R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, and R 3 and R 4 are each independently a hydrogen atom or a methyl group.
- M and n are And each independently represents an integer of 1 to 4.
- X is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 8 carbon atoms.
- Specific examples of the compound represented by the general formula (4) include, for example, compounds represented by the following general formula (4-1) and general formula (4-2).
- R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms.
- M and n are each independently an integer of 1 to 4).
- Examples of the compound represented by the general formula (4-2) include compounds represented by the following general formula.
- aromatic aldehyde having an aromatic ring substituted with an alkyl group having 1 to 8 carbon atoms As described above, by using an aromatic aldehyde having an aromatic ring substituted with an alkyl group having 1 to 8 carbon atoms as the aromatic aldehyde (a2), a radical curable compound having better solvent solubility can be obtained.
- examples of the polycondensate obtained by using an aromatic aldehyde having an aromatic ring substituted with an alkyl group having 1 to 8 carbon atoms include compounds represented by the following general formula.
- R 1 , R 2 and R 5 to R 7 are each independently an alkyl group having 1 to 8 carbon atoms.
- M and n are each independently an integer of 1 to 4; p is an integer of 1 to 5, and q and r are integers of 1 to 7 in total.
- Examples of the compound represented by the general formula (5-2) include compounds represented by the following general formula.
- the polycondensate (A) is isolated from the reaction solution.
- 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, which can express heat resistance that is twice or more that of the conventional one.
- Examples of the method for isolating the polycondensate (A) from the reaction solution in Step 2 include precipitation obtained by adding the reaction solution to a poor solvent (S1) in which the reaction product is insoluble or hardly soluble. After the product is filtered off, the reaction product is dissolved and dissolved in the solvent (S2) that is also mixed with the poor solvent (S1), and the resulting precipitate is again filtered into the poor solvent (S1). Can be mentioned.
- 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 compound of the present invention preferably the radical curable compound of the present invention obtained through the above steps 1 to 3, is added with a polymerization initiator and irradiated with active energy rays or with heat.
- a cured product can be obtained by curing.
- radical curable compound 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) -
- Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4- Thioxanthone compounds such as dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler-ketone and 4,4′-diethylaminobenzophenone; 10-butyl 2-chloro acridone, 2-ethy
- 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 mass, more preferably 0.1 to 15% by mass, and 0.5 to 10 parts by mass with respect to 100 parts by mass of the radical curable compound of the present invention. Part is more preferable.
- a photoinitiator is unnecessary.
- Examples of active energy rays used for curing the radical curable compound 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 compound 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 weight, more preferably 0.1 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight based on 100 parts by weight of the radical curable compound of the present invention. Part by mass is more preferable.
- FIG. 1 shows a chart of IR spectrum
- FIG. 2 shows a chart of 1 H-NMR spectrum
- FIG. 3 shows a chart of 13 C-NMR spectrum.
- Example 2 0.50 g of the radical curable compound (1) obtained in Example 1, 0.05 g of a photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd .; 1-hydroxycyclohexyl phenyl ketone) and 0.5 g of tetrahydrofuran It put into the Schlenk tube and freeze-dried in nitrogen atmosphere. The reactor was sealed and photocured by irradiation with light for 3 hours with a high pressure mercury lamp equipped with a 340 nm bandpass filter. The obtained content was reprecipitated with methanol, and the resulting precipitate was filtered and vacuum dried to obtain 0.35 g of a cured product of the radical curable compound (1).
- a photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd .; 1-hydroxycyclohexyl phenyl ketone)
- tetrahydrofuran tetrahydrofuran
- Example 3 0.50 g of the radical curable compound (1) obtained in Example 1 and a thermal polymerization initiator (azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd .; hereinafter abbreviated as “AIBN”)) 01 g and 0.5 g of dichloroethane were placed in a Schlenk tube and freeze-dried in a nitrogen atmosphere, and the reactor was sealed and thermally cured by heating at 70 ° C. for 12 hours. A reprecipitation operation was performed, and the obtained precipitate was filtered and vacuum dried to obtain 0.21 g of a cured product of the radical curable compound (1).
- AIBN thermal polymerization initiator
- 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.
- Example 6 The same operation as in Example 3 was carried out except that the cresol novolak type epoxy acrylate obtained in Comparative Synthesis Example 3 was used in place of the radical curable compound (1) used in Example 3, and a cresol novolak type epoxy acrylate was used. 0.42 g of a cured product was obtained.
- 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 (Examples 2 and 3) showed no 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
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。
で表されるものである。
アルキル置換フェノール(a1)と芳香族アルデヒド(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で得られた重縮合物(A)を反応溶液中から単離する。
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。
日本分光株式会社製「FT/IR-500」を用いて、KBr錠剤法により測定を行った。
日本電子株式会社製「JNM-LA300」を用いて、試料のDMSO-d6溶液を分析して構造解析を行った。
島津製作所株式会社製「AXIMA-TOF2」を用いて、測定を行った。
冷却管、温度計を備えた100mLの2口フラスコに、2,5-キシレノール3.66g(30mmol)及びベンズアルデヒド1.06g(10mmol)を仕込み、2-エトキシエタノール10mLに溶解させた。氷浴中で冷却しながら硫酸1mLを加えた後、100℃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2,5-キシレノールとベンズアルデヒドとの重縮合物を含む粗生成物を得た。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、真空乾燥を行い淡褐色結晶の重縮合物(A-1)3.08gを得た。この重縮合物(A-1)のIRスペクトル、NMRスペクトル及びMSスペクトルを測定して同定したところ、下記式(3)で表される化合物であることを確認した。
冷却管、温度計を備えた100mLの2口フラスコに、合成例1で得られた重縮合物(A-1)1.66g(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1.80g(20mmol)を30分かけて滴下しながら添加した後、70℃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)1.38gを得た。このラジカル硬化性化合物(1)について、IRスペクトル、NMRスペクトル及びMSスペクトルを測定して同定したところ、下記式(4)で表される化合物であることを確認した。なお、IRスペクトルのチャート図を図1に、1H-NMRスペクトルのチャート図を図2に、13C-NMRスペクトルのチャート図を図3にそれぞれ示す。
(ppm、500MHz、溶媒:DMSO-d6、基準:TMS)
2.0-2.1(12H;Ar-CH 3 ),5.4-5.6(1H;Ar-CH),5.9-6.1(4H;C-CH 2 ),6.2-6.3(2H;CO-CH-C),6.5-7.3(9H;Ar)
(ppm、125MHz、溶媒:DMSO-d6、基準:TMS)
16.0,19.2,49.4,123.4,126.3,126.9,127.9,128.3,129.8,131.7,132.3,135.4,142.3,143.0,164.4
MNa+=463.25
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、実施例2~3及び比較例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、光重合開始剤(BASFジャパン株式会社製「イルガキュア184」;1-ヒドロキシシクロヘキシルフェニルケトン)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時間光を照射して光硬化した。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、ラジカル硬化性化合物(1)の硬化物0.35gを得た。
実施例1で得られたラジカル硬化性化合物(1)0.50gと、熱重合開始剤(アゾビスイソブチロニトリル(和光純薬株式会社製;以下、「AIBN」と略記する。)0.01g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時間加熱を行って熱硬化した。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、ラジカル硬化性化合物(1)の硬化物0.21gを得た。
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。
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。
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。
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。
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。
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。
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 (10)
- 前記R1、R2がそれぞれ独立して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及びn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Xがベンゼン環またはナフタレン環である請求項1記載のラジカル硬化性化合物。
- 前記Xが水素原子の一部ないし全部が炭素原子数1~8のアルキル基で置換されたベンゼン環または水素原子の一部ないし全部が炭素原子数1~8のアルキル基で置換されたナフタレン環である請求項1記載のラジカル硬化性化合物。
- 請求項1~5のいずれか1項記載のラジカル硬化性化合物を活性エネルギー線又は熱で硬化することにより得られることを特徴とする硬化物。
- アルキル置換フェノール(a1)と芳香族アルデヒド(a2)との重縮合物(A)と、(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。
- 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7記載のラジカル硬化性化合物の製造方法。
- 前記芳香族アルデヒド(a2)がベンズアルデヒド、ヒドロキシベンズアルデヒド及びナフトアルデヒドからなる群から選ばれる1種以上のアルデヒドである請求項7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)を反応溶液中から単離する工程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7~9のいずれか1項記載のラジカル硬化性化合物の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020137017924A KR101865634B1 (ko) | 2011-03-08 | 2012-03-05 | 라디칼 경화성 화합물 및 그 경화물, 및 당해 화합물의 제조 방법 |
US14/003,317 US8816033B2 (en) | 2011-03-08 | 2012-03-05 | Radically curable compound, cured product thereof, and method for producing the compound |
EP12754960.8A EP2684900B1 (en) | 2011-03-08 | 2012-03-05 | Radically curable compound, cured product of same, and method for producing same |
CN201280012171.5A CN103415541B (zh) | 2011-03-08 | 2012-03-05 | 自由基固化性化合物及其固化物、以及该化合物的制造方法 |
JP2012548664A JP5305117B2 (ja) | 2011-03-08 | 2012-03-05 | ラジカル硬化性化合物及びその硬化物、並びに該化合物の製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011050128 | 2011-03-08 | ||
JP2011-050128 | 2011-03-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012121195A1 true WO2012121195A1 (ja) | 2012-09-13 |
Family
ID=46798157
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/055523 WO2012121195A1 (ja) | 2011-03-08 | 2012-03-05 | ラジカル硬化性化合物及びその硬化物、並びに該化合物の製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US8816033B2 (ja) |
EP (1) | EP2684900B1 (ja) |
JP (1) | JP5305117B2 (ja) |
KR (1) | KR101865634B1 (ja) |
CN (1) | CN103415541B (ja) |
TW (1) | TWI526455B (ja) |
WO (1) | WO2012121195A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014105335A (ja) * | 2013-11-20 | 2014-06-09 | Dic Corp | アクリル重合体、硬化性組成物、その硬化物、及びレジスト材料用組成物 |
JP2014201691A (ja) * | 2013-04-08 | 2014-10-27 | Dic株式会社 | アクリル系重合体、アクリル系重合体の製造方法及びラジカル硬化性化合物の製造方法 |
JP2015091954A (ja) * | 2012-11-28 | 2015-05-14 | Dic株式会社 | (メタ)アクリロイル基含有樹脂、硬化性組成物、その硬化物、及びレジスト材料 |
JP2016121077A (ja) * | 2014-12-24 | 2016-07-07 | Dic株式会社 | (メタ)アクリレート化合物、(メタ)アクリレート化合物の製造方法、ラジカル硬化性樹脂、ラジカル硬化性樹脂組成物、その硬化物、レジスト材料 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106068292B (zh) * | 2014-03-20 | 2019-02-05 | Dic株式会社 | 酚醛清漆型含酚羟基树脂、其制造方法、固化性组合物、保护剂用组合物及彩色光阻剂 |
JP6796253B2 (ja) * | 2016-04-04 | 2020-12-09 | 日立金属株式会社 | 接着フィルム及びフラット配線材 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09157340A (ja) | 1995-12-08 | 1997-06-17 | Kyoeisha Chem Co Ltd | 新規耐熱性樹脂 |
WO2006132139A1 (ja) * | 2005-06-06 | 2006-12-14 | Mitsubishi Gas Chemical Company, Inc. | レジスト用化合物およびレジスト組成物 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3223104A1 (de) * | 1982-06-21 | 1983-12-22 | Hoechst Ag, 6230 Frankfurt | Photopolymerisierbares gemisch und damit hergestelltes photopolymerisierbares kopiermaterial |
JPH08310985A (ja) * | 1995-05-12 | 1996-11-26 | Nippon Kayaku Co Ltd | ポリフェノール類、エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 |
JP3880912B2 (ja) * | 2002-10-10 | 2007-02-14 | ジャパンエポキシレジン株式会社 | 半導体封止用エポキシ樹脂組成物 |
JP2006132139A (ja) * | 2004-11-04 | 2006-05-25 | Misawa Homes Co Ltd | まちづくり計画地の気候特性把握と緑化方法。 |
JP4630806B2 (ja) * | 2005-12-09 | 2011-02-09 | キヤノン株式会社 | 電子写真感光体、プロセスカートリッジ及び電子写真装置 |
TW200906869A (en) * | 2007-05-30 | 2009-02-16 | Toagosei Co Ltd | Active energy ray curable composition and optical material |
JP2012007086A (ja) * | 2010-06-25 | 2012-01-12 | Sumitomo Bakelite Co Ltd | 封止用樹脂組成物及び電子部品装置 |
-
2012
- 2012-03-05 US US14/003,317 patent/US8816033B2/en active Active
- 2012-03-05 WO PCT/JP2012/055523 patent/WO2012121195A1/ja active Application Filing
- 2012-03-05 CN CN201280012171.5A patent/CN103415541B/zh active Active
- 2012-03-05 JP JP2012548664A patent/JP5305117B2/ja active Active
- 2012-03-05 EP EP12754960.8A patent/EP2684900B1/en active Active
- 2012-03-05 KR KR1020137017924A patent/KR101865634B1/ko active IP Right Grant
- 2012-03-07 TW TW101107583A patent/TWI526455B/zh active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09157340A (ja) | 1995-12-08 | 1997-06-17 | Kyoeisha Chem Co Ltd | 新規耐熱性樹脂 |
WO2006132139A1 (ja) * | 2005-06-06 | 2006-12-14 | Mitsubishi Gas Chemical Company, Inc. | レジスト用化合物およびレジスト組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2684900A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015091954A (ja) * | 2012-11-28 | 2015-05-14 | Dic株式会社 | (メタ)アクリロイル基含有樹脂、硬化性組成物、その硬化物、及びレジスト材料 |
JP2014201691A (ja) * | 2013-04-08 | 2014-10-27 | Dic株式会社 | アクリル系重合体、アクリル系重合体の製造方法及びラジカル硬化性化合物の製造方法 |
JP2014105335A (ja) * | 2013-11-20 | 2014-06-09 | Dic Corp | アクリル重合体、硬化性組成物、その硬化物、及びレジスト材料用組成物 |
JP2016121077A (ja) * | 2014-12-24 | 2016-07-07 | Dic株式会社 | (メタ)アクリレート化合物、(メタ)アクリレート化合物の製造方法、ラジカル硬化性樹脂、ラジカル硬化性樹脂組成物、その硬化物、レジスト材料 |
Also Published As
Publication number | Publication date |
---|---|
US8816033B2 (en) | 2014-08-26 |
TWI526455B (zh) | 2016-03-21 |
EP2684900B1 (en) | 2016-03-02 |
JP5305117B2 (ja) | 2013-10-02 |
US20130338329A1 (en) | 2013-12-19 |
EP2684900A4 (en) | 2014-08-13 |
KR20140031177A (ko) | 2014-03-12 |
TW201242983A (en) | 2012-11-01 |
CN103415541B (zh) | 2015-03-04 |
EP2684900A1 (en) | 2014-01-15 |
KR101865634B1 (ko) | 2018-06-08 |
CN103415541A (zh) | 2013-11-27 |
JPWO2012121195A1 (ja) | 2014-07-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5454749B1 (ja) | 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 | |
JP5892221B2 (ja) | (メタ)アクリロイル基含有樹脂、硬化性組成物、その硬化物、及びレジスト材料 | |
JP5305117B2 (ja) | ラジカル硬化性化合物及びその硬化物、並びに該化合物の製造方法 | |
JP6176477B2 (ja) | アクリル系重合体、アクリル系重合体の製造方法及びラジカル硬化性化合物の製造方法 | |
JP5996412B2 (ja) | ビス(メタ)アクリロイル末端ベンジルエーテル化合物及びその製造方法 | |
JP2009221275A (ja) | 光及び/又は熱硬化性共重合体、硬化性樹脂組成物及び硬化物 | |
JP5741669B2 (ja) | アクリル重合体、硬化性組成物、その硬化物、及びレジスト材料用組成物 | |
JP6435830B2 (ja) | (メタ)アクリレート化合物、ラジカル硬化性樹脂、ラジカル硬化性組成物、その硬化物、レジスト材料、及びラジカル硬化性樹脂の製造方法 | |
JP6464728B2 (ja) | (メタ)アクリレート化合物、(メタ)アクリレート化合物の製造方法、ラジカル硬化性樹脂、ラジカル硬化性樹脂組成物、その硬化物、レジスト材料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2012548664 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12754960 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20137017924 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012754960 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14003317 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |