Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
  • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
  • C07C235/12—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by carboxyl 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
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids

Definitions

• the present invention relates to a blocked isocyanate composition, a (co)polymer, a coating material, a cured product, and a coating film.
• a blocked isocyanate compound is a compound in which the isocyanato group of a compound having an isocyanato group is reacted with a blocking agent to inactivate (block) the reactivity of the isocyanato group. Because the isocyanato group is blocked, the blocked isocyanate compound does not necessarily have to be prepared and stored separately from a compound having a functional group such as an active hydrogen group that reacts with the isocyanato group, and it can be prepared and stored as a single liquid. For this reason, blocked isocyanate compounds are widely used in adhesives, coating agents, molding materials, resin compositions, etc. In addition, water-based resin compositions have been attracting attention in recent years due to growing awareness of global environmental protection.
• Patent Document 1 discloses a polymerizable malonic acid derivative that is a raw material for thermosetting resins used in paints, adhesives, etc.
• Patent Document 1 The polymerizable malonic acid derivative disclosed in Patent Document 1 is in a diluted state in a solution, and there is no suggestion about the storage stability of concentrated polymerizable malonic acid derivatives, so there is room for improvement.
• the present invention was made to solve the above problems, and aims to provide a blocked isocyanate composition with excellent storage stability.
• R 1 represents a hydrogen atom or a methyl group
• R 2 represents a divalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, including a straight chain or a branched chain, which may have an ether bond, or a divalent alicyclic hydrocarbon group or aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a urethane bond
• R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or an arylalkyl group having 6 to 20 carbon atoms.
• R 1 , R 3 and R 4 are defined as the same as the respective symbols in formula (1), and R 2-2 represents a divalent aliphatic saturated hydrocarbon group having 2 to 4 carbon atoms which may have an ether bond.
• R 11 represents -C(COOR 3 )(COOR 4 )R 12
• R 3 and R 4 are as defined by the respective symbols in formula (1).
• R 12 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
• the blocked isocyanate composition (A) according to any one of [1] to [8], wherein the blocking agent is diethyl malonate.
• a (co)polymer (C) obtained by polymerizing the blocked isocyanate composition (A) according to any one of [1] to [9].
• a coating material (F) comprising the (co)polymer (C) according to [10].
• a cured product (G) obtained by curing the (co)polymer (C) according to [10].
• a coating film (H) comprising the cured product (G) according to [12].
• a coating agent (I) comprising the (co)polymer (C) according to [10].
• a photosensitive resin composition (J) comprising the (co)polymer (C) according to [10].
• the present invention provides a blocked isocyanate composition with excellent storage stability.
• (meth)acrylate means either acrylate or methacrylate
• (meth)acrylic acid means either acrylic acid or methacrylic acid
• One embodiment of the present invention is a blocked isocyanate composition (A) containing a blocked isocyanate compound (B) represented by formula (1) and having a blocking agent content of 5 mass% or less.
• R 1 represents a hydrogen atom or a methyl group
• R 2 represents a divalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms which contains a straight chain or a branched chain and which may have an ether bond, or a divalent alicyclic hydrocarbon group or aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a urethane bond
• R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or an arylalkyl group having 6 to 20 carbon atoms.
• the blocked isocyanate compound (B) is represented by the formula (1).
• the blocked isocyanate compound (B) may be a single type alone or a combination of two or more types.
• R 1 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
• R 2 represents a divalent to tetravalent, preferably divalent, aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, including a straight or branched chain that may have an ether bond, or a divalent alicyclic hydrocarbon group or aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a urethane bond.
• R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group or arylalkyl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably a methyl group or an ethyl group, and more particularly preferably an ethyl group.
• the blocked isocyanate compound (B) is preferably represented by formula (1-1), and more preferably represented by formula (1-2).
• R 1 , R 3 and R 4 have the same meanings as the respective symbols in formula (1), and R 2-2 represents a divalent aliphatic saturated hydrocarbon group having 2 to 4 carbon atoms which may have an ether bond.
• R 1 , R 3 and R 4 have the same meanings as the respective symbols in formula (1).
• the blocked isocyanate compound (B) is preferably represented by formula (1-3).
• R 1 and R 2 have the same meanings as the respective symbols in formula (1).
• R 11 represents a residue of a blocking agent for an isocyanato group (R 11 -H) or a salt thereof, which will be described later, and R 11 represents -C(COOR 3 )(COOR 4 )R 12.
• R 12 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, which may have a substituent.
• the method for synthesizing the blocked isocyanate compound (B) is not limited, but an example is a method in which an isocyanate monomer (b-1-1) is reacted with a blocking agent (b-1-2).
• the isocyanate monomer (b-1-1) is preferably represented by the following formula (2). CH 2 ⁇ CR 1 —C( ⁇ O)O—R 2 —NCO (2) [In formula (2), R 1 and R 2 have the same meanings as those in formula (1)]
• Examples of the (meth)acrylic acid ester compound having an isocyanato group represented by formula (2) include a (meth)acrylic acid ester compound having an isocyanato group, and a 1:1 (molar ratio) adduct of a hydroxyl group-containing (meth)acrylate and a diisocyanate compound.
• Examples of (meth)acrylic acid ester compounds having an isocyanato group include 2-(meth)acryloyloxyethyl isocyanate, 3-(meth)acryloyloxy-n-propyl isocyanate, 2-(meth)acryloyloxyisopropyl isocyanate, 4-(meth)acryloyloxy-n-butyl isocyanate, 2-(meth)acryloyloxy-tert-butyl isocyanate, 2-(meth)acryloyloxybutyl-4-isocyanate, and 2-(meth)acryloyloxybutyl-3-isocyanate.
• 2-(meth)acryloyloxybutyl-2-isocyanate 2-(meth)acryloyloxybutyl-1-isocyanate
• 5-(meth)acryloyloxy-n-pentyl isocyanate 6-(meth)acryloyloxy-n-hexyl isocyanate
• 7-(meth)acryloyloxy-n-heptyl isocyanate 2-(isocyanatoethyloxy)ethyl (meth)acrylate, 3-(meth)acryloyloxyphenyl isocyanate, and 4-(meth)acryloyloxyphenyl isocyanate.
• hydroxyl group-containing (meth)acrylate is 2-hydroxyalkyl (meth)acrylate.
• the alkyl group of the 2-hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, and more preferably an ethyl group.
• diisocyanate compounds include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-) xylene diisocyanate, 1,3- (or 1,4-) bis (isocyanatomethyl) cyclohexane, lysine diisocyanate, etc.
• TDI 2,4- (or 2,6-) tolylene diisocyanate
• MDI 4,4'-diphenylmethane diisocyanate
• IPDI 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate
• m- (or p-) xylene diisocyanate 1,3- (or 1,4-) bis (isocyanatomethyl)
• the isocyanate monomer (b-1-1) is preferably 2-(meth)acryloyloxyethyl isocyanate, 2-(isocyanatoethyloxy)ethyl (meth)acrylate, or 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, and more preferably 2-(meth)acryloyloxyethyl isocyanate.
• the blocking agent (b-1-2) in the blocked isocyanate composition (A) is at least one selected from the group consisting of R 11 -H (... formula (3)) and salts of compounds represented by R 11 -H (... formula (3)).
• R 11 is -C(COOR 3 )(COOR 4 )R 12 , where R 3 and R 4 are as defined by the respective symbols in formula (1).
• R 12 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, which may have a substituent.
• the blocking agent (b-1-2) is preferably a malonic acid dialkyl ester, more preferably at least one selected from a malonic acid diester, a malonic acid monoester, and malonic acid, and even more preferably a malonic acid diester.
• Esters of malonic acid monoesters and diesters can be obtained by reacting malonic acid with, for example, an aliphatic alcohol such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, or 2-ethylhexyl alcohol; an alicyclic alcohol such as cyclohexylmethanol; or an alcohol containing an aromatic ring such as benzyl alcohol; or the like, or may be a mixed ester in which the two alcohols are different.
• an aliphatic alcohol such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, or 2-ethylhexyl alcohol
• an alicyclic alcohol such as cyclohexylmethanol
• salts of R 11 -H include salts of metals of Groups 1, 2 and 13 of the periodic table.
• the salts of R 11 -H are preferably salts of sodium, potassium, magnesium, calcium or aluminum, and more preferably salts of sodium or aluminum.
• the content of the blocking agent (b-1-2) in the blocked isocyanate composition (A) is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and preferably 0.0001% by mass or more. If the content of the blocking agent in the blocked isocyanate composition is 5% by mass or less, the polymerization stability of the blocked isocyanate composition (A) is good, which is preferable.
• the content of the blocking agent in the blocked isocyanate composition (A) can be measured by high performance liquid chromatography (hereinafter also referred to as "HPLC").
• blocked isocyanate compound (B) When the blocked isocyanate compound (B) is synthesized using the isocyanate monomer (b-1-1) and the blocking agent (b-1-2) as raw materials, it can be produced by a known method, for example, the following methods (I) to (III).
• (II) A method in which a blocking agent (b-1-2) alone or a suspension of a blocking agent (b-1-2) suspended in an inert solvent is added dropwise to a reaction vessel containing an isocyanate monomer (b-1-1) or a solution of an isocyanate monomer (b-1-1) dissolved in an inert solvent, and the reaction is continued for a while until the reaction is completed.
• (III) A method in which the blocking agent (b-1-2) alone or a suspension of the blocking agent (b-1-2) in an inert solvent and the isocyanate monomer (b-1-1) or a solution of the isocyanate monomer (b-1-1) in an inert solvent are simultaneously added to an empty reaction vessel.
• (I) is preferred since a reaction vessel can be used as a vessel for suspending the inert solvent, reaction catalyst and blocking agent, and there are few restrictions on equipment.
• the blending ratio (molar ratio) of the blocking agent (b-1-2) to the isocyanate monomer (b-1-1) (blocking agent (b-1-2):isocyanate monomer (b-1-1)) is preferably 20:1 to 0.9:1, more preferably 10:1 to 1:1, and even more preferably 8:1 to 2:1.
• the mixing ratio of the blocking agent (b-1-2) is 20:1 or less, crystals are more likely to precipitate, which is preferable. In addition, the reaction tends to proceed more efficiently, which is economically preferable.
• the mixing ratio of the blocking agent (b-1-2) is 0.9:1 or more, the reaction is more likely to be completed, and the time required for completion of the reaction is shorter, which is preferable.
• the reaction temperature of the above reaction varies depending on the type of isocyanate monomer (b-1-1) and blocking agent (b-1-2), the presence or absence of a reaction catalyst, etc., but is preferably from -40°C to 120°C, and more preferably from -15°C to 70°C. If the isocyanate monomer (b-1-1) is 2-acryloyloxyethyl isocyanate, it is more preferably from -10°C to 5°C. If the isocyanate monomer (b-1-1) is 2-methacryloyloxyethyl isocyanate, it is more preferably from 20°C to 60°C.
• a reaction temperature of -40°C or higher is preferred because the reaction proceeds easily.
• the progress of the reaction can be confirmed using high performance liquid chromatography (HPLC).
• reaction catalyst In order to facilitate the above reaction, it is desirable to use a reaction catalyst.
• a reaction catalyst tertiary amines, alkali metal alcoholates such as sodium methoxide and sodium phenolate, and zinc compounds such as zinc acetylacetonate are preferably used, and among these, sodium methoxide and triethylamine are preferred.
• the above reaction catalysts may be used alone or in combination of two or more types.
• the reaction catalyst may be used by dispersing it in a solvent or by dissolving it in a blocking agent.
• the amount of the reaction catalyst used is not particularly limited and may be an amount that allows the reaction to proceed smoothly, but is preferably 0.01 mol or more, more preferably 0.05 mol or more, even more preferably 0.2 mol or more, and preferably 20 mol or less, more preferably 10 mol or less, and even more preferably 5 mol or less, relative to 100 mol of isocyanate monomer (b-1-1). If the amount of the reaction catalyst used is below the above range, the reaction tends to be slow. If the amount of the reaction catalyst used exceeds the above range, it may be difficult to control the reaction. There is no particular limit to the timing of addition of the reaction catalyst.
• the reaction is preferably performed without a solvent, but a solvent may be used.
• a solvent there are no particular limitations on the solvent, so long as it does not react with the isocyanate monomer (b-1-1) or the blocking agent (b-1-2), and examples of the solvent include toluene, xylene, ethyl acetate, tetrahydrofuran, n-butyl acetate, cyclohexanone, and methyl isobutyl ketone. A mixture of some of these solvents may also be used.
• a polymerization inhibitor to the reaction system of the above reaction, within the range that does not impair the effects of the present invention.
• a polymerization inhibitor phenothiazine, p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol (BHT), and other commonly used polymerization inhibitors can be used, with phenothiazine and BHT being particularly suitable in terms of their polymerization inhibition effect.
• the above polymerization inhibitors may be used alone or in combination of two or more types.
• the timing of adding the polymerization inhibitor is not particularly limited, but it is preferable that the polymerization inhibitor is added before all of the isocyanate monomer (b-1-1), blocking agent (b-1-2), and reaction catalyst are added to the reaction vessel. By adding in the above-mentioned order, it is possible to obtain the desired blocked isocyanate compound with high purity and suppress the generation of by-products.
• the reaction is preferably followed by a purification step, such as crystallization, neutralization, extraction, etc.
• crystallization include cooling crystallization, poor solvent crystallization, pressure crystallization, evaporation crystallization, etc., among which cooling crystallization is preferred from the viewpoint of economic merit since it does not require solvent removal.
• neutralization include addition of acid and use of ion exchange resin, among which use of ion exchange resin is preferred, and use of cation exchange resin is more preferred.
• the content of the blocked isocyanate compound (B) in the blocked isocyanate composition (A) is preferably 70% by mass or more, more preferably 85% by mass or more, even more preferably 98% by mass or more, and preferably 99.9% by mass or less. If the content of the blocked isocyanate compound (B) in the blocked isocyanate composition (A) is 70% by mass or more, the stability of the blocked isocyanate composition (A) as crystals is good, which is preferable. The total content of the blocked isocyanate compound (B) and the blocking agent in the blocked isocyanate composition (A) does not exceed 100% by mass.
• the blocked isocyanate composition (A) may contain a dimer of the blocked isocyanate compound (A) (hereinafter also referred to as “dimer”), a decarboxylated form in which either ( COOR3 ) or ( COOR4 ) in formula (1) has been decarboxylated (hereinafter also referred to as “decarboxylated form”), or the like.
• the amount of dimer in the blocked isocyanate composition (A) is preferably 50,000 ppm by mass or less, more preferably 30,000 ppm by mass or less, and even more preferably 10,000 ppm by mass or less, and is preferably 100 ppm by mass or more, and more preferably 500 ppm by mass or more.
• the amount of decarboxylate in the blocked isocyanate composition (A) is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, and even more preferably 1,000 ppm by mass or less, and is preferably 100 ppm by mass or more, and more preferably 500 ppm by mass or more.
• the dimer and decarboxylate in the blocked isocyanate composition (A) can be measured by high performance liquid chromatography.
• the lower detection limit for these is 100 ppm by mass.
• One embodiment of the present invention is a (co)polymer (C) obtained by polymerizing the blocked isocyanate composition (A).
• the (co)polymer (C) contains at least a structural unit (c-1) (hereinafter also referred to as "structural unit (c-1)") derived from the blocked isocyanate compound (B) in the blocked isocyanate composition (A).
• the (co)polymer (C) represents a homopolymer or a copolymer.
• the (co)polymer (C) preferably further comprises, as monomer units, a structural unit (c-2) having a hydroxyl group (hereinafter also referred to as “structural unit (c-2)”), a structural unit (c-3) having an acid group (hereinafter also referred to as “structural unit (c-3)”), and another structural unit (c-4) (hereinafter also referred to as “structural unit (c-4)").
• R 1 , R 2 , R 3 and R 4 have the same meanings as the respective symbols in formula (1).
• the structural unit (c-1) may be of a single type, or a combination of two or more types.
• the content of the structural unit (c-1) in the (co)polymer (C) can be appropriately determined depending on the application of the (co)polymer (C).
• the content of the structural unit (c-1) is preferably 1 to 100 mol%, more preferably 2 to 99 mol%, and even more preferably 5 to 20 mol%.
• the resin composition containing the (co)polymer (C) has better low-temperature curing properties and is likely to form a cured product with better solvent resistance. This is because a sufficient amount of crosslinking is easily ensured by the ester exchange reaction when the resin composition is heat-cured.
• the content of the structural unit (c-1) is 99 mol% or less, the content of the structural unit (c-2) can be sufficiently ensured.
• the (co)polymer (C) in one embodiment of the present invention may contain a structural unit (c-2) having a hydroxyl group.
• the structural unit (c-2) can be appropriately determined depending on the application of the (co)polymer (C).
• the structural unit (c-2) is a structural unit derived from a monomer (cm-2) having a hydroxyl group and an ethylenically unsaturated group (hereinafter also referred to as "monomer (cm-2)").
• the monomer (cm-2) is preferably a hydroxyl group-containing (meth)acrylate, and more preferably a monomer represented by the following formula (5).
• R 21 has the same meaning as R 1 in formula (1), and R 22 is a divalent hydrocarbon group which may contain an ether bond, and a hydrogen atom may be substituted with a substituent.
• the hydrocarbon group as R 22 include an alkylene group, a cycloalkylene group, and an arylene group, and these hydrocarbon groups may be branched.
• R 22 is preferably an alkylene group having 2 to 6 carbon atoms, or an alkylene group having 2 to 6 carbon atoms in which a hydrogen atom is substituted with a substituent such as a hydroxyl group, a phenyl group, a phenoxy group, or a (meth)acryloyloxy group.
• R 22 is more preferably an ethylene group.
• the monomer (cm-2) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, phenoxyhydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, dipropylene glycol mono(meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, etc.
• the monomer (cm-2) is preferably 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, more preferably 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and even more preferably 2-hydroxyethyl (meth)acrylate.
• These monomers (cm-2) may be used alone or in combination of two or more kinds.
• the content of the structural unit (c-2) in the (co)polymer (C) is preferably 0 to 99 mol%, more preferably 2 to 40 mol%, and even more preferably 5 to 20 mol%.
• the content of the structural unit (c-2) is 1 mol% or more, crosslinks are formed by the transesterification reaction with the structural unit (c-1), resulting in a cured product with better low-temperature curing properties and solvent resistance, which is preferable.
• the molar ratio of the structural unit (c-1) to the structural unit (c-2) is preferably from 20:1 to 1:20, more preferably from 5:1 to 1:5, and even more preferably from 3:2 to 2:3. If it is within this range, the structural unit (c-1) and the structural unit (c-2) will crosslink, and a good cured product will be obtained. However, the structural unit (c-2) does not fall under the category of the structural unit (c-1).
• the (co)polymer (C) may contain a structural unit (c-3) having an acid group.
• the structural unit (c-3) can be appropriately determined depending on the application of the (co)polymer (C).
• the structural unit (c-3) is a structural unit derived from an acid group-containing polymerizable monomer (cm-3) (hereinafter also referred to as “monomer (cm-3)”).
• the acid group include a carboxy group (--COOH), a phospho group (--PO(OH) 2 ), a sulfo group (--SO 3 H), etc.
• the carboxy group is preferred from the viewpoints of easy availability of raw materials and solvent resistance.
• the monomer (cm-3) include carboxy group-containing ethylenically unsaturated compounds such as (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, and 2-(meth)acryloyloxyethyl acid phosphate.
• (meth)acrylic acid is preferred from the viewpoints of availability and reactivity.
• These monomers (cm-3) may be used alone or in combination of two or more.
• the content of the structural unit (c-3) in the (co)polymer (C) may be 0%, but when it is contained as a structural unit, it is preferably 1 to 40 mol%, more preferably 5 to 30 mol%, and even more preferably 10 to 20 mol%.
• a content of the structural unit (c-3) of 0 mol% or more is preferable in that sufficient solubility is obtained when an alkali is added, and a content of 40 mol% or less is preferable in that crosslinking is not inhibited.
• the molar ratio of the structural unit (c-1) to the structural unit (c-3) is preferably 20:1 to 1:20, more preferably 5:1 to 1:5, and even more preferably 3:1 to 1:3. Within this range, sufficient alkaline developability can be ensured.
• the (co)polymer (C) may contain another structural unit (c-4) copolymerizable with the structural unit (c-1) as a structural unit contained in the (co)polymer (C).
• the structural unit (c-4) does not include those that fall under the structural units (c-1), (c-2) and (c-3).
• the structural unit (c-4) can be appropriately determined depending on the application of the (co)polymer (C).
• the structural unit (c-4) is a structural unit derived from other monomer (cm-4) (hereinafter also referred to as “monomer (cm-4)”).
• the monomer (cm-4) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, and cyclohexyl (meth)acrylate.
• cyclohexyl (meth)acrylate methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl acrylate isobornyl (meth)acrylate, adamantyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro
• cyclic olefins having a norbornene structure such as pentadec-3-ene
• dienes such as butadiene, isoprene, and chloroprene
• (meth)acrylic acid amides such as (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-diisopropylamide, and (meth)acrylic acid anthracenylamide
• (meth)acrylic acid anilide such as (meth)acrylonitrile, and the like.
• Examples of the monomer include vinyl compounds such as tolyl, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; and monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide.
• (meth)acrylic acid esters and anhydrides of unsaturated carboxylic acids are preferred, and methyl (meth)acrylate is more preferred.
• These monomers (cm-4) may be used alone or in combination of two or more kinds.
• the content of the structural unit (c-4) is preferably 0 to 99 mol%, more preferably 1 to 70 mol%, and even more preferably 60 to 80 mol%. If the content of the structural unit (c-4) is 0 mol% or more, this is preferred because it makes it easier to adjust the Tg. If the content of the structural unit (c-4) is 80 mol% or less, this is preferred because it allows sufficient introduction of blocked isocyanate.
• the molar ratio of the structural unit (c-1) to the structural unit (c-4) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, and even more preferably 5:1 to 1:5. Within this range, the glass transition temperature (Tg) of the (co)polymer can be sufficiently controlled.
• the (co)polymer (C) can be produced by a polymerization reaction of the blocked isocyanate composition (A), preferably a copolymerization reaction of the blocked isocyanate composition (A) with the monomer (cm-2), the monomer (cm-3) or the monomer (cm-4) (hereinafter these reactions are also referred to as "(co)polymerization reactions") in the presence or absence of a polymerization solvent according to a radical polymerization method known in the art.
• the blocked isocyanate composition (A), preferably the monomer, may be dissolved in a solvent as desired, and then a polymerization initiator may be added to the solution, followed by carrying out the (co)polymerization reaction at 50 to 100° C. for 1 to 20 hours.
• a polymerization initiator may be added to the solution, followed by carrying out the (co)polymerization reaction at 50 to 100° C. for 1 to 20 hours.
• the solvent (D) that can be used in the (co)polymerization reaction is not particularly limited as long as it is inert to the reaction, but examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, di ...
• (poly)alkylene glycol monoalkyl ethers such as propylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether;
• (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether.
• ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, acetic acid
• suitable esters include n-propyl, i-propyl acetate, n-buty
• solvents (D) ether-based solvents and alcohol-based solvents are preferred, and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether, and butanol are more preferred. These solvents may be used alone or in combination of two or more kinds.
• the amount of the solvent (D) used in the (co)polymerization reaction is not particularly limited, but is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass, assuming that the total amount of the blocked isocyanate composition (A), preferably the monomer (cm-2), the monomer (cm-3), and the monomer (cm-4) (hereinafter also referred to as "total monomers") charged is 100 parts by mass.
• total monomers preferably the total amount of the blocked isocyanate composition (A), preferably the monomer (cm-2), the monomer (cm-3), and the monomer (cm-4) (hereinafter also referred to as "total monomers") charged is 100 parts by mass.
• the amount of the solvent to 1,000 parts by mass or less, it is possible to suppress the decrease in the molecular weight of the (co)polymer (C) due to the chain transfer effect, and to control the viscosity of the (co)polymer (C) within an appropriate range.
• Polymerization initiators that can be used in this (co)polymerization reaction are not particularly limited, but examples include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, and t-butylperoxy-2-ethylhexanoate. These polymerization initiators may be used alone or in combination of two or more.
• the amount of polymerization initiator used is generally 0.5 to 20 parts by mass, and preferably 1.0 to 10 parts by mass, assuming that the total amount of monomers charged is 100 parts by mass.
• the weight average molecular weight of the (co)polymer (C) in terms of polystyrene is not particularly limited, but the above-mentioned production method can produce a (co)polymer (C) having a weight average molecular weight of preferably 1,000 to 50,000, more preferably 3,000 to 40,000. If the weight average molecular weight of the (co)polymer (C) is 1,000 or more, chipping of the colored pattern after alkaline development when used as a photosensitive resin composition is unlikely to occur. On the other hand, if the weight average molecular weight of the (co)polymer (C) is 50,000 or less, the development time becomes appropriate, ensuring practicality.
• the (co)polymer (C) in one embodiment of the present invention can be suitably used in paints (F), coating agents (I), photosensitive resin compositions (J), etc.
• An example of a photosensitive resin composition is a resist composition for color filters, which preferably contains a colorant.
• One embodiment of the present invention is a cured product (G) obtained by curing the (co)polymer (C).
• the cured product (G) is preferably obtained by crosslinking and curing the (co)polymer (C) by heat.
• the cured product (G) of this embodiment can be suitably used as the coating film (H) which is one embodiment of the present invention, a resist resin for color filters, an adhesive, and the like.
• MOI-DEM blocked isocyanate compositions containing malonic acid 2-[[[[[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester (hereinafter also referred to as "MOI-DEM") will be described below.
• Example 1 128.2 g of diethyl malonate (Tateyama Chemicals Co., Ltd., 0.80 mol), 0.2 g of 2,6-di-t-butylhydroxytoluene (hereinafter also referred to as "BHT") (Oxalis Chemicals Co., Ltd., 0.0009 mol), and 1.0 g of sodium methoxide solution (30 mass% methanol solution, Nippon Soda Co., Ltd., 0.006 mol as sodium methoxide) were added to a 200 mL separable flask equipped with a stirring blade, and the mixture was heated to 50°C under a nitrogen gas atmosphere and stirred for 30 minutes.
• BHT 2,6-di-t-butylhydroxytoluene
• the crystals on the filter paper were washed with 100 g of hexane (Kanto Chemical Co., Ltd., 1.16 mol) and then dried under reduced pressure at room temperature for 4 hours to obtain 53.0 g of purified MOI-DEM crystals with a yield of 84.0%.
• Example 2 Synthesis was performed under the same conditions as in Example 1, except that the amount of diethyl malonate used as a raw material was changed to 96.1 g (0.60 mol) and the molar ratio of diethyl malonate to 2-methacryloyloxyethyl isocyanate was adjusted to the ratio in Table 1, to obtain 45.1 g of purified MOI-DEM crystals at a yield of 71.5%.
• the surface percent purity of the MOI-DEM was 99.2%, and diethyl malonate was not detected.
• Example 3 Synthesis was performed under the same conditions as in Example 1, except that the amount of diethyl malonate used as a raw material was changed to 80.09 g (0.50 mol) and the molar ratio of diethyl malonate to 2-methacryloyloxyethyl isocyanate was adjusted to the ratio in Table 1, to obtain 51.7 g of purified MOI-DEM with a yield of 82.0%.
• the area percent purity of the MOI-DEM was 97.5%, and diethyl malonate was not detected.
• Example 4 Synthesis was performed under the same conditions as in Example 1, except that the amount of diethyl malonate used as a raw material was changed to 64.10 g (0.40 mol) and the molar ratio of diethyl malonate to 2-methacryloyloxyethyl isocyanate was adjusted to the ratio in Table 1, to obtain 45.5 g of purified MOI-DEM with a yield of 72.2%.
• the area percent purity of the MOI-DEM was 98.6%, and diethyl malonate was not detected.
• AOI-DEM blocked isocyanate compositions containing malonic acid 2-[[[[[[[[[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester (hereinafter also referred to as "AOI-DEM") will be described below.
• Example 5 In a 300 mL separable flask equipped with a stirring blade, 181.6 g of diethyl malonate (Tateyama Chemicals Co., Ltd., 1.13 mol), 0.10 g of BHT (Oxalis Chemicals Co., Ltd., 0.0005 mol), and 0.26 g of sodium methoxide solution (30 mass% methanol solution, Nippon Soda Co., Ltd., 0.01 mol as sodium methoxide) were added, and the temperature was lowered to -5°C under a nitrogen gas atmosphere and the mixture was stirred for 30 minutes.
• Example 6 Synthesis was performed in the same manner as in Example 1, except that the temperature during the dropwise addition of 2-acryloyloxyethyl isocyanate and the reaction temperature were changed to -10°C. As a result, 56.5 g of purified AOI-DEM was obtained with a yield of 66.2%. When analyzed in the same manner as in Example 5, the purified AOI-DEM had an areal percent purity of 99.1%, and diethyl malonate was not detected. Furthermore, even when the obtained purified AOI-DEM was stored at room temperature (25°C) for one month, the areal percent purity did not change.
• Example 7 Synthesis was performed in the same manner as in Example 1, except that the temperature during the dropwise addition of 2-acryloyloxyethyl isocyanate and the reaction temperature were changed to 5° C., and 51.4 g of purified AOI-DEM was obtained with a yield of 60.2%.
• the purified AOI-DEM had an areal percent purity of 98.6%, and diethyl malonate was not detected. Furthermore, even when the obtained purified AOI-DEM was stored at room temperature (25° C.) for one month, the areal percent purity did not change.
• Example 8 In a separable flask, 40.0 g (0.28 mol) of 2-acryloyloxyethyl isocyanate, 81.7 g (0.51 mol) of diethyl malonate, and 0.10 g (0.0005 mol) of BHT were added first, and then the temperature was lowered to -10 ° C. and stirred for 30 minutes, after which a mixture of 99.9 g (0.62 mol) of diethyl malonate and 0.26 g of sodium methoxide solution (30 mass% methanol solution, 0.01 mol as sodium methoxide) was added dropwise over 2 hours.
• Example 5 After the subsequent aging, the synthesis was performed in the same manner as in Example 5, and 54.4 g of purified AOI-DEM was obtained with a yield of 63.7%.
• the surface percent purity of the purified AOI-DEM was 98.8%, and diethyl malonate was not detected.
• the surface percent purity did not change even when the obtained purified AOI-DEM was stored at room temperature (25 ° C.) for one month.
• Example 9 In a separable flask, 31.8 g (0.20 mol) of diethyl malonate and 0.05 g of sodium methoxide solution (30 mass% methanol solution, 0.0003 mol as sodium methoxide) were added, and the temperature was lowered to -10 ° C., and after stirring for 30 minutes, a mixture of 149.8 g (0.94 mol) of diethyl malonate and 0.20 g of 30% sodium methoxide methanol solution (0.001 mol as sodium methoxide) and 40.0 g (0.28 mol) of 2-acryloyloxyethyl isocyanate were simultaneously dropped over 2 hours.
• Example 5 After the subsequent aging, the synthesis was performed in the same manner as in Example 5, and 55.9 g of purified AOI-DEM was obtained with a yield of 65.5%.
• the surface percent purity of the purified AOI-DEM was 99.1%, and diethyl malonate was not detected. Furthermore, even when the resulting purified AOI-DEM was stored at room temperature (25° C.) for one month, the surface area purity did not change.
• Examples 1 to 9 unlike Comparative Examples 1 to 4, diethyl malonate was hardly detected in the blocked isocyanate composition (A). Furthermore, in Examples 5 to 9, unlike Comparative Examples 3 and 4, the storage stability at room temperature (25°C) is excellent. This means that the blocked isocyanate composition (A) can be suitably used even when the lead time between production and copolymer synthesis is long.
• Example 10 Synthesis of copolymer
• a stirrer Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 44.8 g of propylene glycol monomethyl ether acetate (manufactured by The Dow Chemical Company) and 7.2 g of normal butanol (Kanto Chemical Reagents) were placed as solvent (D), and the mixture was stirred while replacing with nitrogen gas and heated to 90°C.
• solvent D
• a mixed solution was prepared by mixing 11.8 g (18 mol%) of A) (manufactured by Nippon Shokubai Co., Ltd.), 19.0 g (25 mol%) of methyl methacrylate (MMA) (manufactured by Mitsubishi Chemical Corporation) and 43.5 g (41 mol%) of butyl acrylate (BuA) (manufactured by Nippon Shokubai Co., Ltd.) as other monomers (cm-4), 12.0 g of dimethyl 2,2'-azobis(2-methylpropionate) as a polymerization initiator, and 60.0 g of normal butanol (Kanto Chemical Reagents) as a solvent (D).
• the entire amount of the prepared mixed solution was dropped into propylene glycol monomethyl ether acetate (solvent (D)) in a flask at normal pressure and in a nitrogen gas atmosphere using a dropping funnel over a period of 2 hours. After the dropping was completed, the solution in the flask was stirred while undergoing a polymerization reaction at 90°C for 3 hours to produce a copolymer.
• solvent (D) was added to the reaction solution containing the copolymer thus obtained so that the components other than the solvent (D) were 45% by mass, and the copolymer solution of Example 10 was obtained.
• the weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions, and calculated in terms of polystyrene.
• GPC gel permeation chromatography
• a GPC system manufactured by Shimadzu Corporation was used as the GPC measurement device, and a differential refractive index detector RID-10A was used as the detector.
• three Shodex (registered trademark) LF804 columns manufactured by Showa Denko K.K. and one KF-801 column were connected in series and used.
• the GPC measurement was performed under the conditions of a column temperature of 40° C. and a flow rate of 1.5 mL/min. Tetrahydrofuran was used as the eluent.
• each cured product obtained was measured.
• each glass substrate on which the cured product had been formed was immersed in 100 g of acetone at 25°C for 24 hours.
• the glass substrate was then removed from the acetone and dried at 110°C for 1 hour.
• the mass of the cured product remaining on each dried glass substrate was measured, and the remaining film ratio was calculated using the following formula to evaluate the solvent resistance of the cured product. The closer the remaining film ratio is to 100%, the better the solvent resistance of the cured product.
• Residual film ratio (mass of cured product after immersion in acetone/mass of cured product before immersion in acetone) x 100 (%)
• the pass mark for the evaluation was a residual film rate of 80% or more. The results are shown in Table 5.
• the cured products using the copolymers of Examples 10 to 13 had a residual film rate of 80% or more after acetone immersion, regardless of whether the heating temperature was 80°C or 100°C. This confirmed that the copolymers of Examples 10 to 13 could give cured products that exhibited good solvent resistance even when cured at low temperatures.
• the cured products using the copolymers of Comparative Examples 5 to 8 had a residual film rate of 80% or less after acetone immersion, regardless of whether the heating temperature was 80°C or 100°C, and the solvent resistance was insufficient. This shows that the copolymers of Comparative Examples 5 to 8 do not give cured products with good solvent resistance.
• the blocked isocyanate composition (A) used contains a large amount of diethyl malonate, so some of the 2-hydroxyethyl methacrylate (HEMA) undergoes an ester exchange reaction with diethyl malonate, which is thought to result in the loss of crosslinking points and therefore reduced solvent resistance.
• HEMA 2-hydroxyethyl methacrylate

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