WO2022145338A1 - Method for reducing amount of formaldehyde in liquid composition, and method for producing liquid composition - Google Patents
Method for reducing amount of formaldehyde in liquid composition, and method for producing liquid composition Download PDFInfo
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- WO2022145338A1 WO2022145338A1 PCT/JP2021/047898 JP2021047898W WO2022145338A1 WO 2022145338 A1 WO2022145338 A1 WO 2022145338A1 JP 2021047898 W JP2021047898 W JP 2021047898W WO 2022145338 A1 WO2022145338 A1 WO 2022145338A1
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- WIPO (PCT)
- Prior art keywords
- group
- formaldehyde
- liquid composition
- compound
- composition according
- Prior art date
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 626
- 239000007788 liquid Substances 0.000 title claims abstract description 124
- 239000000203 mixture Substances 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 69
- 230000001603 reducing effect Effects 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 74
- 239000002516 radical scavenger Substances 0.000 claims abstract description 61
- 125000003277 amino group Chemical group 0.000 claims abstract description 60
- 125000003118 aryl group Chemical group 0.000 claims abstract description 33
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 24
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 17
- 125000006239 protecting group Chemical group 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- -1 acrylamide compound Chemical class 0.000 claims description 53
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 claims description 17
- 239000011342 resin composition Substances 0.000 claims description 15
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 10
- 125000004849 alkoxymethyl group Chemical group 0.000 claims description 9
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 8
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 claims description 8
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 8
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical class NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 7
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- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 6
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 claims description 6
- IYGAMTQMILRCCI-UHFFFAOYSA-N 3-aminopropane-1-thiol Chemical compound NCCCS IYGAMTQMILRCCI-UHFFFAOYSA-N 0.000 claims description 6
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 claims description 6
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
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- 239000001294 propane Substances 0.000 claims 2
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- 239000003973 paint Substances 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
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- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Definitions
- the present invention relates to a method for reducing formaldehyde in a liquid composition and a method for producing a liquid composition.
- N-methylol group and N-alkoxymethyl group such as melamine resin and urea resin
- melamine resin and urea resin are used for paints and building materials in advance by reacting between the same molecules or with other resin components.
- melamine derivatives and other methylol compounds have high reactivity and storage stability, and still play an important role in highly functional materials used in electronic devices such as semiconductors.
- a compound having an N-methylol group is obtained by forming an N-methylol group by reacting an amino group with formaldehyde, it often contains a small amount of formaldehyde in principle.
- Formaldehyde is designated as a deleterious substance under the Poisonous and Deleterious Substances Control Law as of November 2020, and is highly toxic to living organisms. It has also been shown to be carcinogenic by the International Agency for Research on Cancer. Furthermore, formaldehyde is released into the air from compounds used in building materials and furniture, causing sick house syndrome, which has become a problem.
- the composition is used to ensure the safety of the manufacturer and the consumer who uses the product. It was necessary to reduce the formaldehyde concentration inside, and especially for molded products and paints, to suppress the release to the gas phase and liquid layer.
- Patent Document 1 discloses that ethylene urea or adipic acid dihydrazide is added to a composition in order to reduce volatile organic molecules such as formaldehyde emitted from a molded product made of a vinyl ester resin. It is considered that the amino group or hydrazide group of the above compound interacts with formaldehyde in the molded product to prevent the emission of formaldehyde.
- Patent Document 2 discloses a method for suppressing formaldehyde emission from a polyacetal resin molded product.
- the effect is promoted by mixing polyethylene wax, polyethylene resin, silicone, and hindered phenol.
- liquid composition such as a liquid resin composition containing formaldehyde
- the operator may be exposed to the volatilized formaldehyde, so that the formaldehyde in the liquid composition can be reduced. It will be important.
- many of the prior patents are for suppressing the release of formaldehyde from molded products, paints, and adhesives, and there are few techniques for reducing the formaldehyde itself present in the liquid composition.
- formaldehyde scavengers sold for the purpose of reducing formaldehyde in liquid compositions are recommended to be added to the composition from a few percent to a maximum of about 20%, which significantly reduces the function of the composition itself. There is a risk of causing it. In particular, even when a plurality of components are added as in Patent Document 2, the risk of affecting the original performance of the composition increases as the types of the added components increase.
- an object of the present invention is to provide a method for reducing formaldehyde in a liquid composition by adding a small amount of a formaldehyde scavenger, and a method for producing a liquid composition using the method.
- the present inventors have included a step of adding a specific formaldehyde scavenger to the liquid composition, so that even a small amount of the addition can be added to the liquid composition.
- a specific formaldehyde scavenger to the liquid composition, so that even a small amount of the addition can be added to the liquid composition.
- a method for reducing formaldehyde in a liquid composition which comprises a step of adding a formaldehyde scavenger to the liquid composition.
- the formaldehyde scavenger has a group A selected from an aromatic amino group and a mercapto group, and is a group selected from an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group.
- liquid composition according to [1] wherein the liquid composition is a liquid composition containing a compound having at least one of an N-methylol group and an N-alkoxymethyl group, and reduces formaldehyde.
- Method. [3] The method for reducing formaldehyde in the liquid composition according to [1] or [2], wherein the group B is selected from an aromatic amino group, an aliphatic amino group and a mercapto group.
- the formaldehyde trapping agent is 2-mercaptoethanol, 2-aminoethanethiol, 1,2-dithioethane, 3-mercaptopropanol, 1-amino-3-mercaptopropane, 1,3-dithiopropane, ⁇ -thio.
- the formaldehyde scavenger is at least one selected from the group consisting of 2-aminoethanethiol, ⁇ -thioglycerol, DL-dithiothreitol, N-acetyl-L-cysteine and 1,8-diaminonaphthalene.
- the amount of the formaldehyde scavenger added in the step of adding the formaldehyde trapping agent is 20 mol equivalents or less with respect to the formaldehyde in the liquid composition before the addition of the formaldehyde scavenger, [1] to [5].
- a method for reducing formaldehyde in the liquid composition according to any one of.
- the compound having at least one of the above N-methylol group and N-alkoxymethyl group is an alkoxymethylated glycol uryl, an alkoxymethylated benzoguanamine, an alkoxymethylated melamine, an N-methylol group or an N-alkoxymethyl group.
- a method for producing a liquid composition which comprises a step of adding a formaldehyde scavenger to the liquid composition.
- the formaldehyde scavenger has a group A selected from an aromatic amino group and a mercapto group, and is a group selected from an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group.
- a method for producing a liquid composition [10] The method for producing a liquid composition according to [9], wherein the liquid composition is a liquid composition containing a compound having at least one of an N-methylol group and an N-alkoxymethyl group. [11] The method for producing a liquid composition according to [9] or [10], wherein the group B is selected from an aromatic amino group, an aliphatic amino group and a mercapto group.
- the formaldehyde trapping agent is 2-mercaptoethanol, 2-aminoethanethiol, 1,2-dithioethane, 3-mercaptopropanol, 1-amino-3-mercaptopropane, 1,3-dithiopropane, ⁇ -thio.
- the formaldehyde scavenger is at least one selected from the group consisting of 2-aminoethanethiol, ⁇ -thioglycerol, DL-dithiothreitol, N-acetyl-L-cysteine and 1,8-diaminonaphthalene.
- the amount of the formaldehyde scavenger added in the step of adding the formaldehyde trapping agent is 20 mol equivalents or less with respect to the formaldehyde in the liquid composition before the addition of the formaldehyde scavenger, [9] to [13]. ].
- the method for producing a liquid composition according to any one of.
- the compound having at least one of the N-methylol group and the N-alkoxymethyl group is an alkoxymethylated glycol uryl, an alkoxymethylated benzoguanamine, an alkoxymethylated melamine, an N-methylol group or an N-alkoxymethyl group.
- the method of the present invention relates to a method for reducing formaldehyde in a liquid composition and a method for producing a liquid composition, which comprises a step of adding a specific formaldehyde scavenger to the liquid composition.
- the formaldehyde trapping agent in the method of the present invention has a group A selected from an aromatic amino group and a mercapto group, and also has an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group. It is a compound having a group B selected from the above, and forming a 5-membered ring or a 6-membered ring by reacting formaldehyde with the group A and the group B.
- the formaldehyde scavenger is a compound having groups A and B.
- the formaldehyde scavenger is a compound that forms a 5-membered ring or a 6-membered ring by reacting formaldehyde with a group A and a group B.
- Group A is a group selected from aromatic amino groups and mercapto groups.
- Group B is a group selected from an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group.
- Examples of the amino group in the aromatic amino group of the group A and the group B and the aliphatic amino group of the group B include a primary amino group and a secondary amino group.
- the aromatic amino group refers to a structure in which an amino group is substituted with an aromatic group.
- the aliphatic amino group refers to a structure in which an amino group is substituted with an aliphatic group.
- the group A and the group B may share one aromatic group.
- 2,3-diaminopyridine has an aminopyridyl group as a group A and a group B which are aromatic amino groups, and a pyridine ring is shared by the groups A and B.
- 1,8-Diaminonaphthalene has an aminonaphthyl group as a group A and a group B which are aromatic amino groups, and a naphthalene ring is shared by the group A and the group B.
- the alkyl a linear or branched alkyl having 1 to 10 carbon atoms is preferable, and for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl.
- N-pentyl 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl, 2,2-Dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl- n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl- n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl- Examples
- the group B is not particularly limited, but is preferably selected from an aromatic amino group, an aliphatic amino group and a mercapto group from the viewpoint of reactivity.
- Hydrazine-based compounds and urea compounds which are conventional formaldehyde scavengers, are said to have the effect of reducing the formaldehyde concentration by reacting with formaldehyde to form imines.
- the formaldehyde scavenger in the method of the present invention has the effect of reducing the formaldehyde concentration by reacting the group A and the group B with formaldehyde to form a 5-membered ring or a 6-membered ring, as described above.
- Have. Cyclic compounds with 5- or 6-membered rings usually tend to be more thermodynamically stable than imines.
- the formaldehyde scavenger in the method of the present invention has higher thermodynamic stability than the conventional formaldehyde scavenger and has excellent formaldehyde scavenging ability, so that the amount added is smaller than that of the conventional formaldehyde scavenger. Has the effect of reducing formaldehyde.
- the formaldehyde scavenger needs to have groups A and B in an arrangement capable of reacting with formaldehyde to form a 5-membered ring or a 6-membered ring. Specifically, the group A and the group B need to be bonded via 2 or 3 carbon atoms.
- the formaldehyde scavenger is preferably one in which the group A and the group B are substituted on the established ring structure.
- 2-Aminoethanethiol, dimercaptopentaerythritol, trimercaptopentaerythritol, tetramercaptopentaeristol, and trimethylolpropane are particularly examples of compounds that are more reactive and easily form 5- or 6-membered rings. preferable.
- These formaldehyde scavengers may be used alone or in combination of two or more.
- the prefabricated ring structure may be a monocyclic compound or a heterocyclic compound. Further, the prefabricated ring structure may be an aromatic ring or a non-aromatic ring, but since the group A and the group B that react with formaldehyde are easily physically close to each other, the prefabricated ring structure is an aromatic ring. It is more preferable to have. And an arrangement capable of forming a 6-membered ring is even more preferable due to thermodynamic stability. Further, from the viewpoint of reactivity with formaldehyde, it is preferable that the 5-membered ring or 6-membered ring does not have a bridging structure.
- the compound in which the group A and the group B are substituted in the aromatic cyclic structure tends to form a 5-membered ring or a 6-membered ring by structurally reacting with formaldehyde, 2,3-diaminopyridine, 3,4- Diaminobenzoic acid and 1,8-diaminonaphthalene are preferred as formaldehyde traps. Further, 1,8-diaminonaphthalene is most preferable because the positions of the groups A and B are fixed on the same plane and have a structure that easily forms a 6-membered ring.
- anthranilamide is described as the most preferable compound for reducing the acetaldehyde content in polyester because it has high reactivity with acetaldehyde, and salicylamide is described as a preferable compound. ..
- A is a group selected from an aromatic amino group and a mercapto group
- B is an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group.
- the group B to be selected is shown.
- R 1 has a prefabricated ring structure and is independently an aromatic ring or a non-aromatic ring.
- the liquid composition containing formaldehyde in the method of the present invention is not particularly limited, but is limited to an N-methylol group (N-CH 2 OH) and an N-alkoxymethyl group (N-CH 2 OR, where R is an alkyl group. ) (Hereinafter, may be referred to as a specific compound) containing at least one of the above.
- the specific compound can not only bond between the same molecules but also react with a compound having an active hydrogen atom such as a hydroxyl group. For this reason, liquid resin compositions using a specific compound as a cross-linking agent between resins have been widely used in molded products, paints, and the like.
- an N-alkoxymethyl group as shown in the following formula 5 in which an alkoxymethyl group is added on the nitrogen of a compound having a functional group different from the N-methylol group or the N-alkoxymethyl group and having an amide bond or a urethane bond.
- a compound having is required to have high properties such as a material for an electronic device because it has a different reaction point or can be used as a monomer of a polymer. It is used for materials.
- liquid resin composition used for materials for electronic devices that require high characteristics is not particularly limited, but is, for example, a patterned retardation material used in a circularly polarized eyeglass type 3D display, or an organic material. Examples thereof include a cured film forming composition useful for producing a retardation material used for a circular polarizing plate used as an antireflection film for an EL display.
- the N of the N-methylol group and the N-alkoxymethyl group includes the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, and the nitrogen-containing heterocycle. Examples thereof include nitrogen atoms bonded to adjacent positions of nitrogen atoms.
- the specific compound includes a nitrogen atom of amide, a nitrogen atom of thioamide, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of urethane, a nitrogen atom bonded to an adjacent position of a nitrogen atom of a nitrogen-containing heterocycle, and the like.
- Examples of the alkyl group in the N-alkoxymethyl group (N-CH 2 OR, where R is an alkyl group) include a linear or branched alkyl group having 1 to 20 carbon atoms, and examples thereof include methyl.
- alkyl group a linear or branched alkyl group having 1 to 6 carbon atoms is preferable.
- Specific examples of the specific compound include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
- alkoxymethylated glycol uryl examples include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycol uryl, 1,3,4,6-tetrakis (butoxymethyl) glycol uryl, 1,3,4. , 6-Tetrax (hydroxymethyl) glycol uryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
- glycoluril compound (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174) manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.), methylated urea resin (Product name: UFR (registered trademark) 65), Butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Co., Ltd. (formerly Dainippon Ink and Chemicals) Examples thereof include urea / formaldehyde-based resins manufactured by Kogyo Co., Ltd. (highly condensed type, trade name: Beccamin (registered trademark) J-300S, P-955, N) and the like.
- alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine and the like.
- Nippon Cytec Industries Co., Ltd. formerly Mitsui Cytec Co., Ltd.
- Cymel registered trademark
- Sanwa Chemical Co., Ltd. trade name: Nicarac (registered trademark) BX- 4000, BX-37, BL-60, BX-55H) and the like.
- alkoxymethylated melamine examples include hexamethoxymethylmelamine and the like.
- Commercially available products include methoxymethyl type melamine compound manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine.
- Compounds (trade name: Mycoat (registered trademark) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd.
- it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group.
- a melamine compound for example, high molecular weight compounds produced from the melamine and benzoguanamine compounds described in US Pat. No. 6,323,310.
- Examples of the commercially available product of the melamine compound include trade name: Cymel (registered trademark) 303 and the like, and the commercially available product of the above benzoguanamine compound includes the product name: Cymel (registered trademark) 1123 (above, Japan Cytec Industries Co., Ltd.). ) (Formerly manufactured by Mitsui Cytec Co., Ltd.).
- an acrylamide compound or a methacrylamide compound substituted with a methylol group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylate, N-ethoxymethylacrylamide, N-butoxymethylmethacrylate or the like and an alkoxymethyl group may be used.
- a methylol group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylate, N-ethoxymethylacrylamide, N-butoxymethylmethacrylate or the like and an alkoxymethyl group
- Polymers produced using it can also be used.
- Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a polymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl.
- Examples thereof include a polymer of methacrylamide and benzyl methacrylate, and a polymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
- a compound having a structure in which at least one of a methylol group and an alkoxymethyl group is bonded to a nitrogen atom of a urethane bond can also be used.
- Examples of such a compound include the following [DM-1], [DM-2], [DM-3], [DM-4] and the like.
- the inclusion of the specific compound in the liquid composition can be confirmed by measuring the liquid composition by, for example, proton nuclear magnetic resonance spectroscopy ( 1 H-NMR), infrared spectroscopy, or the like.
- 1 H-NMR proton nuclear magnetic resonance spectroscopy
- infrared spectroscopy or the like.
- the method of the present invention is a method for reducing formaldehyde in a liquid composition and a method for producing a liquid composition by including a step of adding a formaldehyde scavenger to the liquid composition.
- the method of adding the formaldehyde scavenger to the liquid composition is not particularly limited. Examples of the method of addition include a method of adding the formaldehyde scavenger to the liquid composition as it is, a method of adding a solvent solution or suspension of the formaldehyde scavenger to the liquid composition, and the like. It may be appropriately selected according to the required performance of the molded body.
- a formaldehyde scavenger may be added to the composition at any stage during or after the resin polymerization of the resin composition or at the time of resin molding. .. Further, the liquid resin composition may be added to the solvent solution or suspension of the formaldehyde scavenger.
- the amount of the scavenger added to reduce the formaldehyde concentration by more than half varies depending on the type of formaldehyde scavenger used, so it cannot be explained unconditionally.
- 2-aminoethanethiol and 1,8-diaminonaphthalene which are mentioned as particularly preferable formaldehyde scavengers
- the concentration of formaldehyde reacts with most of the formaldehyde when the molar ratio of formaldehyde present in the liquid composition is 5 equivalents or less. Can be reduced in the range of 70% to 95%.
- the amount of the formaldehyde scavenger added is not particularly limited, but is preferably 0.1 molar equivalent or more with respect to the formaldehyde in the liquid composition before the addition of the formaldehyde scavenger, preferably 0.3. More than a molar equivalent is more preferable, more preferably 0.5 molar equivalent or more, and particularly preferably 1 molar equivalent or more.
- the addition amount is preferably 500 molar equivalents or less, more preferably 100 molar equivalents or less, further preferably 20 molar equivalents or less, and particularly preferably 5 molar equivalents or less.
- the liquid composition may be mixed if necessary.
- the mixing time is not particularly limited, but is usually 5 minutes to 300 minutes, preferably 5 minutes to 120 minutes.
- the mixing temperature is not particularly limited, but is usually 5 to 70 ° C, preferably 5 to 60 ° C.
- a formaldehyde trapping agent in a larger amount than that of formaldehyde in the liquid composition may be added in anticipation of a further trapping effect. Further, it may be used in combination with a formaldehyde scavenger or other additives that have been conventionally used.
- the formaldehyde trapping agent in the method of the present invention may be a silane coupling agent, a surfactant, a rheology adjuster, a pigment, a dye, a storage stabilizer, an antifoaming agent, if necessary, as long as the effect of the present invention is not impaired. It may be added in combination with other additives such as antioxidants.
- the concentration of formaldehyde present in the liquid composition can be quantified by commonly used methods. Specifically, the acetylacetone method, the 2,4-dinitrophenylhydrazine method and the like can be used, and the method is not limited to these methods.
- the acetylacetone method is a method for labeling formaldehyde in a liquid according to the reaction of the following formula 6. Since the formaldehyde derivative absorbs light having a wavelength of 413 nm by the reaction, the formaldehyde concentration can be indirectly quantified by measuring this absorption by an appropriate method.
- An example is a method in which a derivatized solution is poured into a glass cell having a width of 1 cm and the absorbance is directly measured by a spectrophotometer.
- Examples 1 to 7 and Comparative Examples 1 to 6 the effect of reducing the formaldehyde concentration in the liquid composition using the formaldehyde scavenger was evaluated.
- a method for detecting the formaldehyde concentration in Examples and Comparative Examples will be described.
- the mixing ratios described in the following Examples and Comparative Examples are for volume ratios unless otherwise specified. When the mixing ratio is shown in ppm, it is about the mass ratio.
- the acetylacetone method is a method in which a sample solution is mixed with a reaction solution and labeled according to the reaction of the following formula 7.
- 15 g of ammonium acetate, 600 ⁇ l of acetic acid, and 500 ⁇ l of acetylacetone were mixed up to 200 ml with Milli-Q ultrapure water and used as a reaction solution.
- This reaction solution and a liquid composition to which a formaldehyde scavenger was added were mixed, reacted at 50 ° C. for 30 minutes, and then allowed to stand at room temperature for 30 minutes to prepare a formaldehyde derivatized solution.
- a formaldehyde derivative, which is a derivatized compound, was detected in the formaldehyde derivatizing solution.
- formaldehyde Since the formaldehyde derivative absorbs light having a wavelength of 413 nm, formaldehyde can be indirectly detected by measuring the absorbance at this wavelength.
- a spectrophotometer UV-VIS-NIR spectrophotometer UV-3600 manufactured by Shimadzu Corporation
- a formaldehyde derivatizing solution is placed in a 1-centimeter cell glass to have an absorbance at 413 nm. was measured and the amount of reduction in ultraviolet rays was calculated.
- the "formaldehyde detection amount ratio" in Table 1 is based on the absorbance at 413 nm when a standard of 10 ppm formaldehyde is derivatized and detected by a spectrophotometer, and the absorbance in the samples of Examples and Comparative Examples is used as a reference. It shows a multiple. Therefore, in the case of Example 1 in which 100 ppm of 1,8-diaminonaphthalene was added, the absorbance was 0.49 times, and the reduced absorbance of formaldehyde reacted with the formaldehyde scavenger. It is believed that it has been captured.
- Example 2 which is the method of the present invention using 1,8-diaminonaphthalene
- Example 2 which is the method of the present invention using 1,8-diaminonaphthalene
- the same reduction effect was obtained with 1/100 of the addition amount of Comparative Examples 1 and 3. Therefore, the high formaldehyde scavenging ability of the formaldehyde scavenger in the method of the present invention was shown.
- Comparative Example 2 using a diamine compound which does not have a group A and a group B and is not a formaldehyde scavenger according to the method of the present invention had a low formaldehyde reducing effect.
- N-BMAA N-butoxymethylacrylamide
- PBMAA N-butoxymethylacrylamide
- the "formaldehyde detection amount ratio" in Table 2 is based on the absorbance at 413 nm when the formaldehyde extract obtained from the PBMAA solution to which the formaldehyde scavenger is not added is derivatized and detected by a spectrophotometer. ..
- the formaldehyde scavengers of Examples 3 to 7, which are the methods of the present invention were added, the amount of formaldehyde detected was several tens of percent, particularly 1,8-diaminonaphthalene of Example 3 and 2-amino of Example 6.
- ethanethiol was added, the detected amount was successfully reduced by 70% or more.
- the formaldehyde scavengers of Comparative Examples 4 to 6 shown to have the effect of reducing the amount of formaldehyde detected in the prior arts Japanese Patent Laid-Open Nos. 2020-022996 and 2004-352924
- Japanese Patent Laid-Open Nos. 2020-022996 and 2004-352924 Japanese Patent Laid-Open Nos. 2020-022996 and 2004-352924
- it was added in a larger amount than the formaldehyde scavengers of 3 to 7 no further reduction effect was observed. It is considered that this is because the formaldehyde scavengers of Examples 3 to 7 form a 5-membered ring or a 6-membered ring when they react with formaldehyde, and can form a stable structure.
Abstract
Provided is a method for reducing the amount of formaldehyde in a liquid composition, the method including a step for adding a formaldehyde scavenger to the liquid composition. The formaldehyde scavenger is a compound which has a group A selected from among an aromatic amino group and a mercapto group and a group B selected from among an aromatic amino group, an aliphatic amino group, an amino group substituted with a protecting group, a hydroxyl group and a mercapto group. Formaldehyde, the group A and the group B react with each other to form a 5-membered ring or a 6-membered ring.
Description
本発明は、液体組成物中のホルムアルデヒドを低減する方法及び液体組成物の製造方法に関する。
The present invention relates to a method for reducing formaldehyde in a liquid composition and a method for producing a liquid composition.
メラミン樹脂や尿素樹脂のようなＮ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物は、同分子間で反応することや他樹脂成分と反応することにより、予てから塗料や建材に使用される樹脂組成物に添加されてきた。特にメラミン誘導体やその他のメチロール化合物は高い反応性と貯蔵安定性を有し、半導体のような電子デバイスに用いられる高機能性材料において、今日でも重要な役割を担っている。
Compounds having at least one of N-methylol group and N-alkoxymethyl group, such as melamine resin and urea resin, are used for paints and building materials in advance by reacting between the same molecules or with other resin components. Has been added to the resin composition to be made. In particular, melamine derivatives and other methylol compounds have high reactivity and storage stability, and still play an important role in highly functional materials used in electronic devices such as semiconductors.
しかし、Ｎ－メチロール基を有する化合物はアミノ基とホルムアルデヒドが反応することでＮ－メチロール基を形成して得られることから、原理的にホルムアルデヒドを微量に含有することが多い。ホルムアルデヒドは２０２０年１１月現在において毒物劇物取締法の劇物に指定されており、生体に対して高い毒性を有する。また国際がん研究機関により発癌性を有することが示されている。さらに建材や家具に使用された化合物からホルムアルデヒドが空気中に放出され、シックハウス症候群を引き起こすことが問題になっている。従って、Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物を製品に使用する場合は、製造を行う事業者や製品を使用する消費者の安全性を確保するために、組成物中のホルムアルデヒド濃度を低減する、また特に成型品や塗料であれば気相や液層への放出を抑制する必要があった。
However, since a compound having an N-methylol group is obtained by forming an N-methylol group by reacting an amino group with formaldehyde, it often contains a small amount of formaldehyde in principle. Formaldehyde is designated as a deleterious substance under the Poisonous and Deleterious Substances Control Law as of November 2020, and is highly toxic to living organisms. It has also been shown to be carcinogenic by the International Agency for Research on Cancer. Furthermore, formaldehyde is released into the air from compounds used in building materials and furniture, causing sick house syndrome, which has become a problem. Therefore, when a compound having at least one of an N-methylol group and an N-alkoxymethyl group is used in a product, the composition is used to ensure the safety of the manufacturer and the consumer who uses the product. It was necessary to reduce the formaldehyde concentration inside, and especially for molded products and paints, to suppress the release to the gas phase and liquid layer.
ところで、樹脂組成物にホルムアルデヒドと相互作用する化合物を添加することで、樹脂組成物中における濃度の低減及び成型品や塗料からの放出抑制を目指す開発がなされてきた。
By the way, development has been made aiming at reducing the concentration in the resin composition and suppressing the release from molded products and paints by adding a compound that interacts with formaldehyde to the resin composition.
特許文献１は、ビニルエステル樹脂からなる成型品から放散するホルムアルデヒド等の揮発性有機分子を低減するために、組成物中にエチレン尿素やアジピン酸ジヒドラジドを添加することが開示されている。上記化合物のアミノ基又はヒドラジド基が成型品中のホルムアルデヒドと相互作用することでホルムアルデヒドの放散を防止していると考えられる。
Patent Document 1 discloses that ethylene urea or adipic acid dihydrazide is added to a composition in order to reduce volatile organic molecules such as formaldehyde emitted from a molded product made of a vinyl ester resin. It is considered that the amino group or hydrazide group of the above compound interacts with formaldehyde in the molded product to prevent the emission of formaldehyde.
特許文献２は、ポリアセタール樹脂成型品からのホルムアルデヒド放出を抑制する方法が開示されている。この文献ではホルムアルデヒドを低減する効果を高めるためにホルムアルデヒド捕捉剤として使用されるジヒドラジド化合物以外にもポリエチレンワックス、ポリエチレン樹脂、シリコーン、ヒンダードフェノールを混ぜることで効果を促進している。
Patent Document 2 discloses a method for suppressing formaldehyde emission from a polyacetal resin molded product. In this document, in addition to the dihydrazide compound used as a formaldehyde scavenger to enhance the effect of reducing formaldehyde, the effect is promoted by mixing polyethylene wax, polyethylene resin, silicone, and hindered phenol.
ホルムアルデヒドを含有する液体の樹脂組成物等の液体組成物を用いて製造を行う場合には、作業者が揮発したホルムアルデヒドに暴露する可能性があるため、液体組成物中のホルムアルデヒドを低減することが重要となる。しかし先行特許の多くは成型品や塗料、接着剤からのホルムアルデヒドの放出を抑制するためのものが多く、液体組成物中に存在するホルムアルデヒドそのものを低減するための技術は少ない。
When manufacturing is performed using a liquid composition such as a liquid resin composition containing formaldehyde, the operator may be exposed to the volatilized formaldehyde, so that the formaldehyde in the liquid composition can be reduced. It will be important. However, many of the prior patents are for suppressing the release of formaldehyde from molded products, paints, and adhesives, and there are few techniques for reducing the formaldehyde itself present in the liquid composition.
また、液体組成物中のホルムアルデヒドを低減する目的で販売されているホルムアルデヒド捕捉剤では組成物に数％から多くて２０％程度まで添加することが推奨されており、組成物自体の機能を著しく低下させる恐れがある。特に、特許文献２のように複数の成分を添加する場合においても添加した成分の種類が増えるほど組成物本来の性能に影響が及ぶリスクが高まる。
In addition, formaldehyde scavengers sold for the purpose of reducing formaldehyde in liquid compositions are recommended to be added to the composition from a few percent to a maximum of about 20%, which significantly reduces the function of the composition itself. There is a risk of causing it. In particular, even when a plurality of components are added as in Patent Document 2, the risk of affecting the original performance of the composition increases as the types of the added components increase.
従って、ホルムアルデヒド捕捉剤の添加量がごく少量であっても、液体組成物中に含まれるホルムアルデヒドの量を十分に低減することができる方法が求められている。また、ホルムアルデヒド捕捉剤における単一成分の添加によって、液体組成物中のホルムアルデヒドの量を十分に低減することができる方法が求められている。さらに液体組成物の中でも、特にＮ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物を含有する液体組成物中のホルムアルデヒドを十分に低減する方法が求められている。
Therefore, there is a demand for a method capable of sufficiently reducing the amount of formaldehyde contained in the liquid composition even if the amount of the formaldehyde scavenger added is very small. Further, there is a demand for a method capable of sufficiently reducing the amount of formaldehyde in a liquid composition by adding a single component in a formaldehyde scavenger. Further, among the liquid compositions, there is a need for a method for sufficiently reducing formaldehyde in the liquid composition containing a compound having at least one of an N-methylol group and an N-alkoxymethyl group.
本発明は、以上の知見や検討結果に基づいてなされたものである。すなわち、本発明の目的は、液体組成物中のホルムアルデヒドを、少量のホルムアルデヒド捕捉剤の添加により低減する方法及び当該方法を用いて液体組成物を製造する方法を提供することを目的とする。
The present invention has been made based on the above findings and study results. That is, an object of the present invention is to provide a method for reducing formaldehyde in a liquid composition by adding a small amount of a formaldehyde scavenger, and a method for producing a liquid composition using the method.
本発明者らは上記目的を達成するために鋭意検討を重ねた結果、特定のホルムアルデヒド捕捉剤を、液体組成物に添加する工程を含むことにより、少量の添加であっても液体組成物中のホルムアルデヒド濃度を十分に低減することが可能であることを発見し、以下の要旨を有する本発明を完成させた。
As a result of diligent studies to achieve the above object, the present inventors have included a step of adding a specific formaldehyde scavenger to the liquid composition, so that even a small amount of the addition can be added to the liquid composition. We have discovered that it is possible to sufficiently reduce the formaldehyde concentration, and completed the present invention having the following gist.
すなわち、本発明は以下を包含する。
［１］ ホルムアルデヒド捕捉剤を液体組成物に添加する工程を含む、液体組成物中のホルムアルデヒドを低減する方法であって、
上記ホルムアルデヒド捕捉剤は、芳香族アミノ基及びメルカプト基から選ばれる基Ａを有するとともに、芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基Ｂを有し、ホルムアルデヒドと上記基Ａと上記基Ｂとが反応することにより５員環又は６員環を形成する化合物である、
液体組成物中のホルムアルデヒドを低減する方法。
［２］ 上記液体組成物が、Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物を含有する液体組成物である、［１］に記載の液体組成物中のホルムアルデヒドを低減する方法。
［３］ 上記基Ｂが、芳香族アミノ基、脂肪族アミノ基及びメルカプト基から選ばれる、［１］又は［２］に記載の液体組成物中のホルムアルデヒドを低減する方法。
［４］ 上記ホルムアルデヒド捕捉剤は、２－メルカプトエタノール、２－アミノエタンチオール、１，２－ジチオエタン、３－メルカプトプロパノール、１－アミノ－３－メルカプトプロパン、１，３－ジチオプロパン、α－チオグリセロール、ジメルカプロール、ジメルカプトペンタエリストール、トリメルカプトペンタエリストール、テトラメルカプトペンタエリストール、トリメルカプトトリメチロールプロパン、ＤＬ－ジチオトレイトール、Ｌ－システイン、Ｎ－アセチル－Ｌ－システイン、２，３－ジアミノピリジン、３，４－ジアミノ安息香酸及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、［１］又は［２］に記載の液体組成物中のホルムアルデヒドを低減する方法。
［５］ 上記ホルムアルデヒド捕捉剤は、２－アミノエタンチオール、α－チオグリセロール、ＤＬ－ジチオトレイトール、Ｎ－アセチル－Ｌ－システイン及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、［４］に記載の液体組成物中のホルムアルデヒドを低減する方法。
［６］ 上記添加する工程における上記ホルムアルデヒド捕捉剤の添加量は、上記ホルムアルデヒド捕捉剤を添加する前の上記液体組成物中におけるホルムアルデヒドに対して、２０モル当量以下である、［１］～［５］のいずれかに記載の液体組成物中のホルムアルデヒドを低減する方法。
［７］ 上記Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物は、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、アルコキシメチル化メラミン、Ｎ－メチロール基又はＮ－アルコキシメチル基で置換されたアクリルアミド化合物もしくはメタクリルアミド化合物を使用して製造されるポリマー並びにウレタン結合の窒素原子にメチロール基及びアルコキシメチル基の少なくともいずれかが結合した構造を有する化合物からなる群から選択される少なくとも一種の化合物である、［２］～［６］のいずれかに記載の液体組成物中のホルムアルデヒドを低減する方法。
［８］ 上記液体組成物は、電子デバイス用の液体の樹脂組成物である、［１］～［７］のいずれかに記載の組成物中のホルムアルデヒドを低減する方法。
［９］ ホルムアルデヒド捕捉剤を液体組成物に添加する工程を含む、液体組成物の製造方法であって、
上記ホルムアルデヒド捕捉剤は、芳香族アミノ基及びメルカプト基から選ばれる基Ａを有するとともに、芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基Ｂを有し、ホルムアルデヒドと上記基Ａと上記基Ｂとが反応することにより５員環又は６員環を形成する化合物である、
液体組成物の製造方法。
［１０］ 上記液体組成物が、Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物を含有する液体組成物である、［９］に記載の液体組成物の製造方法。
［１１］ 上記基Ｂが、芳香族アミノ基、脂肪族アミノ基及びメルカプト基から選ばれる、［９］又は［１０］に記載の液体組成物の製造方法。
［１２］ 上記ホルムアルデヒド捕捉剤は、２－メルカプトエタノール、２－アミノエタンチオール、１，２－ジチオエタン、３－メルカプトプロパノール、１－アミノ－３－メルカプトプロパン、１，３－ジチオプロパン、α－チオグリセロール、ジメルカプロール、ジメルカプトペンタエリストール、トリメルカプトペンタエリストール、テトラメルカプトペンタエリストール、トリメルカプトトリメチロールプロパン、ＤＬ－ジチオトレイトール、Ｌ－システイン、Ｎ－アセチル－Ｌ－システイン、２，３－ジアミノピリジン、３，４－ジアミノ安息香酸及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、［９］又は［１０］に記載の液体組成物の製造方法。
［１３］ 上記ホルムアルデヒド捕捉剤は、２－アミノエタンチオール、α－チオグリセロール、ＤＬ－ジチオトレイトール、Ｎ－アセチル－Ｌ－システイン及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、［１２］に記載の液体組成物の製造方法。
［１４］ 上記添加する工程における上記ホルムアルデヒド捕捉剤の添加量は、上記ホルムアルデヒド捕捉剤を添加する前の上記液体組成物中におけるホルムアルデヒドに対して、２０モル当量以下である、［９］～［１３］のいずれかに記載の液体組成物の製造方法。
［１５］ 上記Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物は、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、アルコキシメチル化メラミン、Ｎ－メチロール基又はＮ－アルコキシメチル基で置換されたアクリルアミド化合物もしくはメタクリルアミド化合物を使用して製造されるポリマー並びにウレタン結合の窒素原子にメチロール基及びアルコキシメチル基の少なくともいずれかが結合した構造を有する化合物からなる群から選択される少なくとも一種の化合物である、［１０］～［１４］のいずれかに記載の液体組成物の製造方法。
［１６］ 上記液体組成物は、電子デバイス用の液体の樹脂組成物である、［９］～［１５］のいずれかに記載の液体組成物の製造方法。 That is, the present invention includes the following.
[1] A method for reducing formaldehyde in a liquid composition, which comprises a step of adding a formaldehyde scavenger to the liquid composition.
The formaldehyde scavenger has a group A selected from an aromatic amino group and a mercapto group, and is a group selected from an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group. A compound having B and forming a 5-membered ring or a 6-membered ring by reacting formaldehyde with the group A and the group B.
A method of reducing formaldehyde in a liquid composition.
[2] The liquid composition according to [1], wherein the liquid composition is a liquid composition containing a compound having at least one of an N-methylol group and an N-alkoxymethyl group, and reduces formaldehyde. Method.
[3] The method for reducing formaldehyde in the liquid composition according to [1] or [2], wherein the group B is selected from an aromatic amino group, an aliphatic amino group and a mercapto group.
[4] The formaldehyde trapping agent is 2-mercaptoethanol, 2-aminoethanethiol, 1,2-dithioethane, 3-mercaptopropanol, 1-amino-3-mercaptopropane, 1,3-dithiopropane, α-thio. Gglycerol, dimercaprol, dimercaptopentaerystol, trimercaptopentaeristol, tetramercaptopentaeristol, trimercaptotrimethylolpropane, DL-dithiothreitol, L-cysteine, N-acetyl-L-cysteine, 2, Formaldehyde in the liquid composition according to [1] or [2], which is at least one compound selected from the group consisting of 3-diaminopyridine, 3,4-diaminobenzoic acid and 1,8-diaminonaphthalene. How to reduce.
[5] The formaldehyde scavenger is at least one selected from the group consisting of 2-aminoethanethiol, α-thioglycerol, DL-dithiothreitol, N-acetyl-L-cysteine and 1,8-diaminonaphthalene. The method for reducing formaldehyde in the liquid composition according to [4], which is a compound.
[6] The amount of the formaldehyde scavenger added in the step of adding the formaldehyde trapping agent is 20 mol equivalents or less with respect to the formaldehyde in the liquid composition before the addition of the formaldehyde scavenger, [1] to [5]. ] A method for reducing formaldehyde in the liquid composition according to any one of.
[7] The compound having at least one of the above N-methylol group and N-alkoxymethyl group is an alkoxymethylated glycol uryl, an alkoxymethylated benzoguanamine, an alkoxymethylated melamine, an N-methylol group or an N-alkoxymethyl group. At least one selected from the group consisting of a polymer produced using a substituted acrylamide compound or a methacrylamide compound and a compound having a structure in which at least one of a methylol group and an alkoxymethyl group is bonded to a nitrogen atom of a urethane bond. The method for reducing formaldehyde in the liquid composition according to any one of [2] to [6], which is a compound of.
[8] The method for reducing formaldehyde in the composition according to any one of [1] to [7], wherein the liquid composition is a liquid resin composition for electronic devices.
[9] A method for producing a liquid composition, which comprises a step of adding a formaldehyde scavenger to the liquid composition.
The formaldehyde scavenger has a group A selected from an aromatic amino group and a mercapto group, and is a group selected from an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group. A compound having B and forming a 5-membered ring or a 6-membered ring by reacting formaldehyde with the group A and the group B.
A method for producing a liquid composition.
[10] The method for producing a liquid composition according to [9], wherein the liquid composition is a liquid composition containing a compound having at least one of an N-methylol group and an N-alkoxymethyl group.
[11] The method for producing a liquid composition according to [9] or [10], wherein the group B is selected from an aromatic amino group, an aliphatic amino group and a mercapto group.
[12] The formaldehyde trapping agent is 2-mercaptoethanol, 2-aminoethanethiol, 1,2-dithioethane, 3-mercaptopropanol, 1-amino-3-mercaptopropane, 1,3-dithiopropane, α-thio. Gglycerol, dimercaprol, dimercaptopentaerystol, trimercaptopentaeristol, tetramercaptopentaeristol, trimercaptotrimethylolpropane, DL-dithiothreitol, L-cysteine, N-acetyl-L-cysteine, 2, The method for producing a liquid composition according to [9] or [10], which is at least one compound selected from the group consisting of 3-diaminopyridine, 3,4-diaminobenzoic acid and 1,8-diaminonaphthalene.
[13] The formaldehyde scavenger is at least one selected from the group consisting of 2-aminoethanethiol, α-thioglycerol, DL-dithiothreitol, N-acetyl-L-cysteine and 1,8-diaminonaphthalene. The method for producing a liquid composition according to [12], which is a compound.
[14] The amount of the formaldehyde scavenger added in the step of adding the formaldehyde trapping agent is 20 mol equivalents or less with respect to the formaldehyde in the liquid composition before the addition of the formaldehyde scavenger, [9] to [13]. ]. The method for producing a liquid composition according to any one of.
[15] The compound having at least one of the N-methylol group and the N-alkoxymethyl group is an alkoxymethylated glycol uryl, an alkoxymethylated benzoguanamine, an alkoxymethylated melamine, an N-methylol group or an N-alkoxymethyl group. At least one selected from the group consisting of a polymer produced using a substituted acrylamide compound or a methacrylamide compound and a compound having a structure in which at least one of a methylol group and an alkoxymethyl group is bonded to a nitrogen atom of a urethane bond. The method for producing a liquid composition according to any one of [10] to [14], which is a compound of.
[16] The method for producing a liquid composition according to any one of [9] to [15], wherein the liquid composition is a liquid resin composition for an electronic device.
［１］ ホルムアルデヒド捕捉剤を液体組成物に添加する工程を含む、液体組成物中のホルムアルデヒドを低減する方法であって、
上記ホルムアルデヒド捕捉剤は、芳香族アミノ基及びメルカプト基から選ばれる基Ａを有するとともに、芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基Ｂを有し、ホルムアルデヒドと上記基Ａと上記基Ｂとが反応することにより５員環又は６員環を形成する化合物である、
液体組成物中のホルムアルデヒドを低減する方法。
［２］ 上記液体組成物が、Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物を含有する液体組成物である、［１］に記載の液体組成物中のホルムアルデヒドを低減する方法。
［３］ 上記基Ｂが、芳香族アミノ基、脂肪族アミノ基及びメルカプト基から選ばれる、［１］又は［２］に記載の液体組成物中のホルムアルデヒドを低減する方法。
［４］ 上記ホルムアルデヒド捕捉剤は、２－メルカプトエタノール、２－アミノエタンチオール、１，２－ジチオエタン、３－メルカプトプロパノール、１－アミノ－３－メルカプトプロパン、１，３－ジチオプロパン、α－チオグリセロール、ジメルカプロール、ジメルカプトペンタエリストール、トリメルカプトペンタエリストール、テトラメルカプトペンタエリストール、トリメルカプトトリメチロールプロパン、ＤＬ－ジチオトレイトール、Ｌ－システイン、Ｎ－アセチル－Ｌ－システイン、２，３－ジアミノピリジン、３，４－ジアミノ安息香酸及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、［１］又は［２］に記載の液体組成物中のホルムアルデヒドを低減する方法。
［５］ 上記ホルムアルデヒド捕捉剤は、２－アミノエタンチオール、α－チオグリセロール、ＤＬ－ジチオトレイトール、Ｎ－アセチル－Ｌ－システイン及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、［４］に記載の液体組成物中のホルムアルデヒドを低減する方法。
［６］ 上記添加する工程における上記ホルムアルデヒド捕捉剤の添加量は、上記ホルムアルデヒド捕捉剤を添加する前の上記液体組成物中におけるホルムアルデヒドに対して、２０モル当量以下である、［１］～［５］のいずれかに記載の液体組成物中のホルムアルデヒドを低減する方法。
［７］ 上記Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物は、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、アルコキシメチル化メラミン、Ｎ－メチロール基又はＮ－アルコキシメチル基で置換されたアクリルアミド化合物もしくはメタクリルアミド化合物を使用して製造されるポリマー並びにウレタン結合の窒素原子にメチロール基及びアルコキシメチル基の少なくともいずれかが結合した構造を有する化合物からなる群から選択される少なくとも一種の化合物である、［２］～［６］のいずれかに記載の液体組成物中のホルムアルデヒドを低減する方法。
［８］ 上記液体組成物は、電子デバイス用の液体の樹脂組成物である、［１］～［７］のいずれかに記載の組成物中のホルムアルデヒドを低減する方法。
［９］ ホルムアルデヒド捕捉剤を液体組成物に添加する工程を含む、液体組成物の製造方法であって、
上記ホルムアルデヒド捕捉剤は、芳香族アミノ基及びメルカプト基から選ばれる基Ａを有するとともに、芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基Ｂを有し、ホルムアルデヒドと上記基Ａと上記基Ｂとが反応することにより５員環又は６員環を形成する化合物である、
液体組成物の製造方法。
［１０］ 上記液体組成物が、Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物を含有する液体組成物である、［９］に記載の液体組成物の製造方法。
［１１］ 上記基Ｂが、芳香族アミノ基、脂肪族アミノ基及びメルカプト基から選ばれる、［９］又は［１０］に記載の液体組成物の製造方法。
［１２］ 上記ホルムアルデヒド捕捉剤は、２－メルカプトエタノール、２－アミノエタンチオール、１，２－ジチオエタン、３－メルカプトプロパノール、１－アミノ－３－メルカプトプロパン、１，３－ジチオプロパン、α－チオグリセロール、ジメルカプロール、ジメルカプトペンタエリストール、トリメルカプトペンタエリストール、テトラメルカプトペンタエリストール、トリメルカプトトリメチロールプロパン、ＤＬ－ジチオトレイトール、Ｌ－システイン、Ｎ－アセチル－Ｌ－システイン、２，３－ジアミノピリジン、３，４－ジアミノ安息香酸及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、［９］又は［１０］に記載の液体組成物の製造方法。
［１３］ 上記ホルムアルデヒド捕捉剤は、２－アミノエタンチオール、α－チオグリセロール、ＤＬ－ジチオトレイトール、Ｎ－アセチル－Ｌ－システイン及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、［１２］に記載の液体組成物の製造方法。
［１４］ 上記添加する工程における上記ホルムアルデヒド捕捉剤の添加量は、上記ホルムアルデヒド捕捉剤を添加する前の上記液体組成物中におけるホルムアルデヒドに対して、２０モル当量以下である、［９］～［１３］のいずれかに記載の液体組成物の製造方法。
［１５］ 上記Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物は、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、アルコキシメチル化メラミン、Ｎ－メチロール基又はＮ－アルコキシメチル基で置換されたアクリルアミド化合物もしくはメタクリルアミド化合物を使用して製造されるポリマー並びにウレタン結合の窒素原子にメチロール基及びアルコキシメチル基の少なくともいずれかが結合した構造を有する化合物からなる群から選択される少なくとも一種の化合物である、［１０］～［１４］のいずれかに記載の液体組成物の製造方法。
［１６］ 上記液体組成物は、電子デバイス用の液体の樹脂組成物である、［９］～［１５］のいずれかに記載の液体組成物の製造方法。 That is, the present invention includes the following.
[1] A method for reducing formaldehyde in a liquid composition, which comprises a step of adding a formaldehyde scavenger to the liquid composition.
The formaldehyde scavenger has a group A selected from an aromatic amino group and a mercapto group, and is a group selected from an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group. A compound having B and forming a 5-membered ring or a 6-membered ring by reacting formaldehyde with the group A and the group B.
A method of reducing formaldehyde in a liquid composition.
[2] The liquid composition according to [1], wherein the liquid composition is a liquid composition containing a compound having at least one of an N-methylol group and an N-alkoxymethyl group, and reduces formaldehyde. Method.
[3] The method for reducing formaldehyde in the liquid composition according to [1] or [2], wherein the group B is selected from an aromatic amino group, an aliphatic amino group and a mercapto group.
[4] The formaldehyde trapping agent is 2-mercaptoethanol, 2-aminoethanethiol, 1,2-dithioethane, 3-mercaptopropanol, 1-amino-3-mercaptopropane, 1,3-dithiopropane, α-thio. Gglycerol, dimercaprol, dimercaptopentaerystol, trimercaptopentaeristol, tetramercaptopentaeristol, trimercaptotrimethylolpropane, DL-dithiothreitol, L-cysteine, N-acetyl-L-cysteine, 2, Formaldehyde in the liquid composition according to [1] or [2], which is at least one compound selected from the group consisting of 3-diaminopyridine, 3,4-diaminobenzoic acid and 1,8-diaminonaphthalene. How to reduce.
[5] The formaldehyde scavenger is at least one selected from the group consisting of 2-aminoethanethiol, α-thioglycerol, DL-dithiothreitol, N-acetyl-L-cysteine and 1,8-diaminonaphthalene. The method for reducing formaldehyde in the liquid composition according to [4], which is a compound.
[6] The amount of the formaldehyde scavenger added in the step of adding the formaldehyde trapping agent is 20 mol equivalents or less with respect to the formaldehyde in the liquid composition before the addition of the formaldehyde scavenger, [1] to [5]. ] A method for reducing formaldehyde in the liquid composition according to any one of.
[7] The compound having at least one of the above N-methylol group and N-alkoxymethyl group is an alkoxymethylated glycol uryl, an alkoxymethylated benzoguanamine, an alkoxymethylated melamine, an N-methylol group or an N-alkoxymethyl group. At least one selected from the group consisting of a polymer produced using a substituted acrylamide compound or a methacrylamide compound and a compound having a structure in which at least one of a methylol group and an alkoxymethyl group is bonded to a nitrogen atom of a urethane bond. The method for reducing formaldehyde in the liquid composition according to any one of [2] to [6], which is a compound of.
[8] The method for reducing formaldehyde in the composition according to any one of [1] to [7], wherein the liquid composition is a liquid resin composition for electronic devices.
[9] A method for producing a liquid composition, which comprises a step of adding a formaldehyde scavenger to the liquid composition.
The formaldehyde scavenger has a group A selected from an aromatic amino group and a mercapto group, and is a group selected from an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group. A compound having B and forming a 5-membered ring or a 6-membered ring by reacting formaldehyde with the group A and the group B.
A method for producing a liquid composition.
[10] The method for producing a liquid composition according to [9], wherein the liquid composition is a liquid composition containing a compound having at least one of an N-methylol group and an N-alkoxymethyl group.
[11] The method for producing a liquid composition according to [9] or [10], wherein the group B is selected from an aromatic amino group, an aliphatic amino group and a mercapto group.
[12] The formaldehyde trapping agent is 2-mercaptoethanol, 2-aminoethanethiol, 1,2-dithioethane, 3-mercaptopropanol, 1-amino-3-mercaptopropane, 1,3-dithiopropane, α-thio. Gglycerol, dimercaprol, dimercaptopentaerystol, trimercaptopentaeristol, tetramercaptopentaeristol, trimercaptotrimethylolpropane, DL-dithiothreitol, L-cysteine, N-acetyl-L-cysteine, 2, The method for producing a liquid composition according to [9] or [10], which is at least one compound selected from the group consisting of 3-diaminopyridine, 3,4-diaminobenzoic acid and 1,8-diaminonaphthalene.
[13] The formaldehyde scavenger is at least one selected from the group consisting of 2-aminoethanethiol, α-thioglycerol, DL-dithiothreitol, N-acetyl-L-cysteine and 1,8-diaminonaphthalene. The method for producing a liquid composition according to [12], which is a compound.
[14] The amount of the formaldehyde scavenger added in the step of adding the formaldehyde trapping agent is 20 mol equivalents or less with respect to the formaldehyde in the liquid composition before the addition of the formaldehyde scavenger, [9] to [13]. ]. The method for producing a liquid composition according to any one of.
[15] The compound having at least one of the N-methylol group and the N-alkoxymethyl group is an alkoxymethylated glycol uryl, an alkoxymethylated benzoguanamine, an alkoxymethylated melamine, an N-methylol group or an N-alkoxymethyl group. At least one selected from the group consisting of a polymer produced using a substituted acrylamide compound or a methacrylamide compound and a compound having a structure in which at least one of a methylol group and an alkoxymethyl group is bonded to a nitrogen atom of a urethane bond. The method for producing a liquid composition according to any one of [10] to [14], which is a compound of.
[16] The method for producing a liquid composition according to any one of [9] to [15], wherein the liquid composition is a liquid resin composition for an electronic device.
本発明によれば、液体組成物中のホルムアルデヒドを、少量のホルムアルデヒド捕捉剤の添加により低減する方法及び当該方法を用いて液体組成物を製造する方法を提供することを提供することができる。
INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for reducing formaldehyde in a liquid composition by adding a small amount of a formaldehyde scavenger and a method for producing a liquid composition using the method.
以下、本発明について詳細に説明する。なお、以下に記載する構成要件の説明は、本発明を説明するための例示であり、本発明はこれらの内容に限定されるものではない。
Hereinafter, the present invention will be described in detail. The description of the constituent elements described below is an example for explaining the present invention, and the present invention is not limited to these contents.
本発明の方法は、特定のホルムアルデヒド捕捉剤を、液体組成物に添加する工程を含む、液体組成物中のホルムアルデヒドを低減する方法及び液体組成物の製造方法に関する。
The method of the present invention relates to a method for reducing formaldehyde in a liquid composition and a method for producing a liquid composition, which comprises a step of adding a specific formaldehyde scavenger to the liquid composition.
以下、本発明の方法におけるホルムアルデヒド捕捉剤及び液体組成物について説明した後、液体組成物中のホルムアルデヒドを低減する方法及び液体組成物の製造方法について説明する。
Hereinafter, the formaldehyde scavenger and the liquid composition in the method of the present invention will be described, and then a method for reducing formaldehyde in the liquid composition and a method for producing the liquid composition will be described.
（ホルムアルデヒド捕捉剤）
本発明の方法におけるホルムアルデヒド捕捉剤は、芳香族アミノ基及びメルカプト基から選ばれる基Ａを有するとともに、芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基Ｂを有し、ホルムアルデヒドと前記基Ａと前記基Ｂとが反応することにより５員環又は６員環を形成する化合物である。
言い換えれば、ホルムアルデヒド捕捉剤は、基Ａ及び基Ｂを有する化合物である。
ホルムアルデヒド捕捉剤は、ホルムアルデヒドと基Ａと基Ｂとが反応することにより５員環又は６員環を形成する化合物である。
基Ａは、芳香族アミノ基及びメルカプト基から選ばれる基である。
基Ｂは、芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基である。 (Formaldehyde scavenger)
The formaldehyde trapping agent in the method of the present invention has a group A selected from an aromatic amino group and a mercapto group, and also has an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group. It is a compound having a group B selected from the above, and forming a 5-membered ring or a 6-membered ring by reacting formaldehyde with the group A and the group B.
In other words, the formaldehyde scavenger is a compound having groups A and B.
The formaldehyde scavenger is a compound that forms a 5-membered ring or a 6-membered ring by reacting formaldehyde with a group A and a group B.
Group A is a group selected from aromatic amino groups and mercapto groups.
Group B is a group selected from an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group.
本発明の方法におけるホルムアルデヒド捕捉剤は、芳香族アミノ基及びメルカプト基から選ばれる基Ａを有するとともに、芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基Ｂを有し、ホルムアルデヒドと前記基Ａと前記基Ｂとが反応することにより５員環又は６員環を形成する化合物である。
言い換えれば、ホルムアルデヒド捕捉剤は、基Ａ及び基Ｂを有する化合物である。
ホルムアルデヒド捕捉剤は、ホルムアルデヒドと基Ａと基Ｂとが反応することにより５員環又は６員環を形成する化合物である。
基Ａは、芳香族アミノ基及びメルカプト基から選ばれる基である。
基Ｂは、芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基である。 (Formaldehyde scavenger)
The formaldehyde trapping agent in the method of the present invention has a group A selected from an aromatic amino group and a mercapto group, and also has an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group. It is a compound having a group B selected from the above, and forming a 5-membered ring or a 6-membered ring by reacting formaldehyde with the group A and the group B.
In other words, the formaldehyde scavenger is a compound having groups A and B.
The formaldehyde scavenger is a compound that forms a 5-membered ring or a 6-membered ring by reacting formaldehyde with a group A and a group B.
Group A is a group selected from aromatic amino groups and mercapto groups.
Group B is a group selected from an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group.
理論に縛られるものではないが、本発明の方法におけるホルムアルデヒド捕捉剤を、ホルムアルデヒドを含有する液体組成物に添加すると、まず、求核性に優れる上記基Ａとホルムアルデヒドとの反応が生ずるものと推定される。その後、求核性に優れるものの上記基Ａと比較して求核性が同じである又は低い傾向にある上記基Ｂが、上記基Ａとホルムアルデヒドとの反応物と反応することにより、熱力学的に安定な５員環又は６員環を形成するものと推定される。これにより、本発明の方法におけるホルムアルデヒド捕捉剤は、ホルムアルデヒド捕捉能に優れるものと推定される。
Although not bound by theory, it is presumed that when the formaldehyde scavenger in the method of the present invention is added to a liquid composition containing formaldehyde, a reaction between the above-mentioned group A having excellent nucleophilicity and formaldehyde first occurs. Will be done. After that, the group B, which has excellent nucleophilicity but tends to have the same or lower nucleophilicity as the group A, reacts with the reactant of the group A and formaldehyde, thereby thermodynamically. It is presumed to form a stable 5-membered ring or 6-membered ring. Therefore, it is presumed that the formaldehyde scavenger in the method of the present invention has excellent formaldehyde scavenging ability.
上記基Ａ及び上記基Ｂの芳香族アミノ基並びに上記基Ｂの脂肪族アミノ基におけるアミノ基としては、１級アミノ基及び２級アミノ基が挙げられる。
芳香族アミノ基とは、芳香族基にアミノ基が置換された構造を指す。
脂肪族アミノ基とは、脂肪族基にアミノ基が置換された構造を指す。
ホルムアルデヒド捕捉剤において基Ａ及び基Ｂの両方が芳香族アミノ基の場合、基Ａ及び基Ｂは一つの芳香族基を共有していてもよい。例えば、２，３－ジアミノピリジンは芳香族アミノ基である基Ａ及び基Ｂとしてアミノピリジル基を有し、ピリジン環は基Ａ及び基Ｂに共有されている。１，８－ジアミノナフタレンは芳香族アミノ基である基Ａ及び基Ｂとしてアミノナフチル基を有し、ナフタレン環は基Ａ及び基Ｂに共有されている。 Examples of the amino group in the aromatic amino group of the group A and the group B and the aliphatic amino group of the group B include a primary amino group and a secondary amino group.
The aromatic amino group refers to a structure in which an amino group is substituted with an aromatic group.
The aliphatic amino group refers to a structure in which an amino group is substituted with an aliphatic group.
When both the group A and the group B are aromatic amino groups in the formaldehyde scavenger, the group A and the group B may share one aromatic group. For example, 2,3-diaminopyridine has an aminopyridyl group as a group A and a group B which are aromatic amino groups, and a pyridine ring is shared by the groups A and B. 1,8-Diaminonaphthalene has an aminonaphthyl group as a group A and a group B which are aromatic amino groups, and a naphthalene ring is shared by the group A and the group B.
芳香族アミノ基とは、芳香族基にアミノ基が置換された構造を指す。
脂肪族アミノ基とは、脂肪族基にアミノ基が置換された構造を指す。
ホルムアルデヒド捕捉剤において基Ａ及び基Ｂの両方が芳香族アミノ基の場合、基Ａ及び基Ｂは一つの芳香族基を共有していてもよい。例えば、２，３－ジアミノピリジンは芳香族アミノ基である基Ａ及び基Ｂとしてアミノピリジル基を有し、ピリジン環は基Ａ及び基Ｂに共有されている。１，８－ジアミノナフタレンは芳香族アミノ基である基Ａ及び基Ｂとしてアミノナフチル基を有し、ナフタレン環は基Ａ及び基Ｂに共有されている。 Examples of the amino group in the aromatic amino group of the group A and the group B and the aliphatic amino group of the group B include a primary amino group and a secondary amino group.
The aromatic amino group refers to a structure in which an amino group is substituted with an aromatic group.
The aliphatic amino group refers to a structure in which an amino group is substituted with an aliphatic group.
When both the group A and the group B are aromatic amino groups in the formaldehyde scavenger, the group A and the group B may share one aromatic group. For example, 2,3-diaminopyridine has an aminopyridyl group as a group A and a group B which are aromatic amino groups, and a pyridine ring is shared by the groups A and B. 1,8-Diaminonaphthalene has an aminonaphthyl group as a group A and a group B which are aromatic amino groups, and a naphthalene ring is shared by the group A and the group B.
上記基Ｂの保護基で置換されたアミノ基における保護基としては、通常アミンの保護基として使用されるものであれば特に限定されないが、中でも－Ｃ（＝Ｏ）－アルキルが好ましい。アルキルとしては、直鎖又は分枝を有する炭素原子数１乃至１０のアルキルが好ましく、例えばメチル、エチル、ｎ－プロピル、ｉ－プロピル、ｎ－ブチル、ｉ－ブチル、ｓ－ブチル、ｔ－ブチル、ｎ－ペンチル、１－メチル－ｎ－ブチル、２－メチル－ｎ－ブチル、３－メチル－ｎ－ブチル、１，１－ジメチル－ｎ－プロピル基、１，２－ジメチル－ｎ－プロピル、２，２－ジメチル－ｎ－プロピル、１－エチル－ｎ－プロピル、ｎ－ヘキシル、１－メチル－ｎ－ペンチル、２－メチル－ｎ－ペンチル、３－メチル－ｎ－ペンチル、４－メチル－ｎ－ペンチル、１，１－ジメチル－ｎ－ブチル、１，２－ジメチル－ｎ－ブチル、１，３－ジメチル－ｎ－ブチル、２，２－ジメチル－ｎ－ブチル、２，３－ジメチル－ｎ－ブチル、３，３－ジメチル－ｎ－ブチル、１－エチル－ｎ－ブチル、２－エチル－ｎ－ブチル、１，１，２－トリメチル－ｎ－プロピル、１，２，２－トリメチル－ｎ－プロピル、１－エチル－１－メチル－ｎ－プロピル及び１－エチル－２－メチル－ｎ－プロピル等が挙げられる。
The protecting group in the amino group substituted with the protecting group of the group B is not particularly limited as long as it is usually used as a protecting group for amines, but -C (= O) -alkyl is preferable. As the alkyl, a linear or branched alkyl having 1 to 10 carbon atoms is preferable, and for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl. , N-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl, 2,2-Dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl- n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl- n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl- Examples thereof include n-propyl, 1-ethyl-1-methyl-n-propyl and 1-ethyl-2-methyl-n-propyl.
上記基Ｂとしては、特に制限されるものではないが、反応性の観点から、芳香族アミノ基、脂肪族アミノ基及びメルカプト基から選ばれるのが好ましい。
The group B is not particularly limited, but is preferably selected from an aromatic amino group, an aliphatic amino group and a mercapto group from the viewpoint of reactivity.
従来のホルムアルデヒド捕捉剤であるヒドラジン系の化合物及び尿素化合物等は、ホルムアルデヒドと反応してイミンを形成することにより、ホルムアルデヒド濃度を低減する効果を有するとされている。これに対して本発明の方法におけるホルムアルデヒド捕捉剤は、上述したように、基Ａ及び基Ｂがホルムアルデヒドと反応し、５員環又は６員環を形成することにより、ホルムアルデヒド濃度を低減する効果を有する。５員環又は６員環の環式化合物は、通常、イミンよりも熱力学的に安定である傾向がある。このため、本発明の方法におけるホルムアルデヒド捕捉剤は、従来のホルムアルデヒド捕捉剤と比較して熱力学的安定性が高く、ホルムアルデヒド捕捉能に優れるため、従来のホルムアルデヒド捕捉剤と比較してより少ない添加量でホルムアルデヒドを低減する効果を有する。
Hydrazine-based compounds and urea compounds, which are conventional formaldehyde scavengers, are said to have the effect of reducing the formaldehyde concentration by reacting with formaldehyde to form imines. On the other hand, the formaldehyde scavenger in the method of the present invention has the effect of reducing the formaldehyde concentration by reacting the group A and the group B with formaldehyde to form a 5-membered ring or a 6-membered ring, as described above. Have. Cyclic compounds with 5- or 6-membered rings usually tend to be more thermodynamically stable than imines. Therefore, the formaldehyde scavenger in the method of the present invention has higher thermodynamic stability than the conventional formaldehyde scavenger and has excellent formaldehyde scavenging ability, so that the amount added is smaller than that of the conventional formaldehyde scavenger. Has the effect of reducing formaldehyde.
ホルムアルデヒド捕捉剤は、ホルムアルデヒドと反応し５員環又は６員環を形成することができる配置に基Ａ及び基Ｂを有する必要がある。具体的には、基Ａと基Ｂとが、２又は３の炭素原子を介して結合されている必要がある。ホルムアルデヒド捕捉剤は、基Ａ及び基Ｂが既成環構造上に置換されたものであることが好ましい。
The formaldehyde scavenger needs to have groups A and B in an arrangement capable of reacting with formaldehyde to form a 5-membered ring or a 6-membered ring. Specifically, the group A and the group B need to be bonded via 2 or 3 carbon atoms. The formaldehyde scavenger is preferably one in which the group A and the group B are substituted on the established ring structure.
上記の条件を満たし液体組成物中のホルムアルデヒドを低減する効果を有するホルムアルデヒド捕捉剤の具体例としては、２－メルカプトエタノール、２－アミノエタンチオール、１，２－ジチオエタン、３－メルカプトプロパノール、１－アミノ－３－メルカプトプロパン、１，３－ジチオプロパン、α－チオグリセロール、ジメルカプロール、ジメルカプトペンタエリストール、トリメルカプトペンタエリストール、テトラメルカプトペンタエリストール、トリメルカプトトリメチロールプロパン、ＤＬ－ジチオトレイトール、Ｌ－システイン、Ｎ－アセチル－Ｌ－システイン、２，３－ジアミノピリジン、３，４－ジアミノ安息香酸、１，８－ジアミノナフタレンが含まれる。特にメルカプト基を有するという点から２－アミノエタンチオール、１，２－ジチオエタン、３－メルカプトプロパノール、１－アミノ－３－メルカプトプロパン、１，３－ジチオプロパン、α－チオグリセロール、ジメルカプロール、ジメルカプトペンタエリストール、トリメルカプトペンタエリストール、テトラメルカプトペンタエリストール、トリメルカプトトリメチロールプロパン、ＤＬ－ジチオトレイトール、Ｌ－システイン、Ｎ－アセチル－Ｌ－システインが好ましい。さらにより反応性が高く５員環又は６員環を形成しやすい化合物として２－アミノエタンチオール、ジメルカプトペンタエリストール、トリメルカプトペンタエリストール、テトラメルカプトペンタエリストール、トリメルカプトトリメチロールプロパンが特に好ましい。これらのホルムアルデヒド捕捉剤は、単独で又は２種以上を組み合わせて用いても良い。
Specific examples of the formaldehyde trapping agent that satisfies the above conditions and has the effect of reducing formaldehyde in the liquid composition include 2-mercaptoethanol, 2-aminoethanethiol, 1,2-dithiothreitol, 3-mercaptopropanol, and 1-. Amino-3-mercaptopropane, 1,3-dithiopropane, α-thioglycerol, dimercaprol, dimercaptopentaesterol, trimercaptopentaeristol, tetramercaptopentaeristol, trimercaptotrimethylolpropane, DL-dithio Includes Treitol, L-cysteine, N-acetyl-L-cysteine, 2,3-diaminopyridine, 3,4-diaminobenzoic acid, 1,8-diaminonaphthalene. 2-Aminoethanethiol, 1,2-dithioethritol, 3-mercaptopropanol, 1-amino-3-mercaptopropane, 1,3-dithiopropane, α-thioglycerol, dimercaprol, especially in terms of having a mercapto group. Dimercaptopentaerythritol, trimercaptopentaeristol, tetramercaptopentaeristol, trimercaptotrimethylolpropane, DL-dithiothritol, L-cysteine, N-acetyl-L-cysteine are preferred. 2-Aminoethanethiol, dimercaptopentaerythritol, trimercaptopentaerythritol, tetramercaptopentaeristol, and trimethylolpropane are particularly examples of compounds that are more reactive and easily form 5- or 6-membered rings. preferable. These formaldehyde scavengers may be used alone or in combination of two or more.
また別の観点として、既成環構造は単環式化合物であっても良く、また複素環式化合物であっても良い。さらに既成環構造は芳香環であっても良く、非芳香環であっても良いが、ホルムアルデヒドと反応する基Ａと基Ｂとが物理的に近接しやすいことから、既成環構造は芳香環であることがより好ましい。そして熱力学的な安定性から６員環を形成し得る配置がより一層好ましい。また、ホルムアルデドとの反応性の観点からは、５員環又は６員環の環式化合物が橋かけ構造を有さないのが好ましい。芳香族環式構造に基Ａ及び基Ｂが置換された化合物は構造的にホルムアルデヒドと反応することで５員環又は６員環を形成しやすいため、２，３－ジアミノピリジン、３，４－ジアミノ安息香酸、１，８－ジアミノナフタレンがホルムアルデヒド捕捉剤として好ましい。さらに基Ａ及び基Ｂの位置が同一平面上に固定され、６員環を形成しやすい構造を有することから、１，８－ジアミノナフタレンが最も好ましい。
From another viewpoint, the prefabricated ring structure may be a monocyclic compound or a heterocyclic compound. Further, the prefabricated ring structure may be an aromatic ring or a non-aromatic ring, but since the group A and the group B that react with formaldehyde are easily physically close to each other, the prefabricated ring structure is an aromatic ring. It is more preferable to have. And an arrangement capable of forming a 6-membered ring is even more preferable due to thermodynamic stability. Further, from the viewpoint of reactivity with formaldehyde, it is preferable that the 5-membered ring or 6-membered ring does not have a bridging structure. Since the compound in which the group A and the group B are substituted in the aromatic cyclic structure tends to form a 5-membered ring or a 6-membered ring by structurally reacting with formaldehyde, 2,3-diaminopyridine, 3,4- Diaminobenzoic acid and 1,8-diaminonaphthalene are preferred as formaldehyde traps. Further, 1,8-diaminonaphthalene is most preferable because the positions of the groups A and B are fixed on the same plane and have a structure that easily forms a 6-membered ring.
上記の条件を満たさないため、ホルムアルデヒドと反応し５員環又は６員環を形成し得ず、液体組成物中のホルムアルデヒド含量を低減する効果を有さない化合物の具体例としては、１，２－エタンジオール、２－アミノエタノール、Ｎ－メチルエタノールアミン、１，２－ジアミノエタン、１，３－プロパンジオール、３－アミノプロパノール、１，３－ジアミノプロパン、グリセロール、マロンアミド、アントラニルアミド、サリチルアミド等が挙げられる。なお、先行文献（国際公開第２００１／０６２８３８号）では、アセトアルデヒドと高い反応性を有することからポリエステル中のアセトデヒド含有量を低減する最も好ましい化合物としてアントラニルアミド、好ましい化合物としてサリチルアミドが記載されている。
Specific examples of compounds that do not satisfy the above conditions and therefore cannot react with formaldehyde to form a 5-membered ring or a 6-membered ring and do not have the effect of reducing the formaldehyde content in the liquid composition include 1,2. -Etandiol, 2-aminoethanol, N-methylethanolamine, 1,2-diaminoethane, 1,3-propanediol, 3-aminopropanol, 1,3-diaminopropane, glycerol, malonamide, anthranilamide, salicylamide And so on. In the preceding document (International Publication No. 2001/062838), anthranilamide is described as the most preferable compound for reducing the acetaldehyde content in polyester because it has high reactivity with acetaldehyde, and salicylamide is described as a preferable compound. ..
本発明の方法におけるホルムアルデヒド捕捉剤と、液体組成物中のホルムアルデヒドとの反応の一例を下記に示す。
An example of the reaction between the formaldehyde scavenger in the method of the present invention and formaldehyde in the liquid composition is shown below.
上記式１乃至式４中、Ａは芳香族アミノ基及びメルカプト基から選ばれる基Ａ、Ｂは芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基Ｂを示す。上記式３及び４において、Ｒ１は既成環構造であり、それぞれ独立して芳香環または非芳香環である。
In the above formulas 1 to 4, A is a group selected from an aromatic amino group and a mercapto group, and B is an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group. The group B to be selected is shown. In the above formulas 3 and 4, R 1 has a prefabricated ring structure and is independently an aromatic ring or a non-aromatic ring.
（ホルムアルデヒドを含有する液体組成物）
本発明の方法におけるホルムアルデヒドを含有する液体組成物は、特に限定さないが、Ｎ－メチロール基（Ｎ－ＣＨ２ＯＨ）及びＮ－アルコキシメチル基（Ｎ－ＣＨ２ＯＲ、ここでＲはアルキル基）の少なくともいずれかを有する化合物（以下、特定化合物と称する場合がある）を含有する液体組成物が好ましい。特定化合物は同分子間で結合するだけでなく、水酸基のような活性水素原子を有する化合物とも反応し得る。このため、特定化合物を樹脂間の架橋剤として用いた液体の樹脂組成物が、成型品や塗料等に広く使用されてきた。さらにＮ－メチロール基又はＮ－アルコキシメチル基とは別の官能基を持ち、アミド結合又はウレタン結合を有する化合物の窒素上に、アルコキシメチル基を付加した下記式５のようなＮ－アルコキシメチル基を有する化合物では、活性水素原子との高い反応性だけでなく、別の反応点を有する、もしくは重合体のモノマーとして使用可能である点から、電子デバイス用材料のような高度な特性を要求される材料に使用されている。そのため下記式５のような化合物を含有する液体の樹脂組成物がホルムアルデヒドを含有する場合、樹脂組成物の高い機能が失われない範囲でホルムアルデヒド濃度を低減する必要があり、本発明を利用されることがより一層望まれる。高度な特性が要求される電子デバイス用材料に使用されている液体の樹脂組成物としては、特に制限されないが、例えば、円偏光メガネ方式の３Ｄディスプレイに用いられるパターニングされた位相差材や、有機ＥＬディスプレイの反射防止膜として使用される円偏光板に用いられる位相差材を作製するのに有用な硬化膜形成組成物が挙げられる。 (Liquid composition containing formaldehyde)
The liquid composition containing formaldehyde in the method of the present invention is not particularly limited, but is limited to an N-methylol group (N-CH 2 OH) and an N-alkoxymethyl group (N-CH 2 OR, where R is an alkyl group. ) (Hereinafter, may be referred to as a specific compound) containing at least one of the above. The specific compound can not only bond between the same molecules but also react with a compound having an active hydrogen atom such as a hydroxyl group. For this reason, liquid resin compositions using a specific compound as a cross-linking agent between resins have been widely used in molded products, paints, and the like. Further, an N-alkoxymethyl group as shown in the following formula 5 in which an alkoxymethyl group is added on the nitrogen of a compound having a functional group different from the N-methylol group or the N-alkoxymethyl group and having an amide bond or a urethane bond. In addition to having high reactivity with an active hydrogen atom, a compound having is required to have high properties such as a material for an electronic device because it has a different reaction point or can be used as a monomer of a polymer. It is used for materials. Therefore, when a liquid resin composition containing a compound such as the following formula 5 contains formaldehyde, it is necessary to reduce the formaldehyde concentration within a range in which the high function of the resin composition is not lost, and the present invention is utilized. Is even more desired. The liquid resin composition used for materials for electronic devices that require high characteristics is not particularly limited, but is, for example, a patterned retardation material used in a circularly polarized eyeglass type 3D display, or an organic material. Examples thereof include a cured film forming composition useful for producing a retardation material used for a circular polarizing plate used as an antireflection film for an EL display.
本発明の方法におけるホルムアルデヒドを含有する液体組成物は、特に限定さないが、Ｎ－メチロール基（Ｎ－ＣＨ２ＯＨ）及びＮ－アルコキシメチル基（Ｎ－ＣＨ２ＯＲ、ここでＲはアルキル基）の少なくともいずれかを有する化合物（以下、特定化合物と称する場合がある）を含有する液体組成物が好ましい。特定化合物は同分子間で結合するだけでなく、水酸基のような活性水素原子を有する化合物とも反応し得る。このため、特定化合物を樹脂間の架橋剤として用いた液体の樹脂組成物が、成型品や塗料等に広く使用されてきた。さらにＮ－メチロール基又はＮ－アルコキシメチル基とは別の官能基を持ち、アミド結合又はウレタン結合を有する化合物の窒素上に、アルコキシメチル基を付加した下記式５のようなＮ－アルコキシメチル基を有する化合物では、活性水素原子との高い反応性だけでなく、別の反応点を有する、もしくは重合体のモノマーとして使用可能である点から、電子デバイス用材料のような高度な特性を要求される材料に使用されている。そのため下記式５のような化合物を含有する液体の樹脂組成物がホルムアルデヒドを含有する場合、樹脂組成物の高い機能が失われない範囲でホルムアルデヒド濃度を低減する必要があり、本発明を利用されることがより一層望まれる。高度な特性が要求される電子デバイス用材料に使用されている液体の樹脂組成物としては、特に制限されないが、例えば、円偏光メガネ方式の３Ｄディスプレイに用いられるパターニングされた位相差材や、有機ＥＬディスプレイの反射防止膜として使用される円偏光板に用いられる位相差材を作製するのに有用な硬化膜形成組成物が挙げられる。 (Liquid composition containing formaldehyde)
The liquid composition containing formaldehyde in the method of the present invention is not particularly limited, but is limited to an N-methylol group (N-CH 2 OH) and an N-alkoxymethyl group (N-CH 2 OR, where R is an alkyl group. ) (Hereinafter, may be referred to as a specific compound) containing at least one of the above. The specific compound can not only bond between the same molecules but also react with a compound having an active hydrogen atom such as a hydroxyl group. For this reason, liquid resin compositions using a specific compound as a cross-linking agent between resins have been widely used in molded products, paints, and the like. Further, an N-alkoxymethyl group as shown in the following formula 5 in which an alkoxymethyl group is added on the nitrogen of a compound having a functional group different from the N-methylol group or the N-alkoxymethyl group and having an amide bond or a urethane bond. In addition to having high reactivity with an active hydrogen atom, a compound having is required to have high properties such as a material for an electronic device because it has a different reaction point or can be used as a monomer of a polymer. It is used for materials. Therefore, when a liquid resin composition containing a compound such as the following formula 5 contains formaldehyde, it is necessary to reduce the formaldehyde concentration within a range in which the high function of the resin composition is not lost, and the present invention is utilized. Is even more desired. The liquid resin composition used for materials for electronic devices that require high characteristics is not particularly limited, but is, for example, a patterned retardation material used in a circularly polarized eyeglass type 3D display, or an organic material. Examples thereof include a cured film forming composition useful for producing a retardation material used for a circular polarizing plate used as an antireflection film for an EL display.
＜Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物＞
Ｎ－メチロール基及びＮ－アルコキシメチル基のＮ、すなわち窒素原子としては、アミドの窒素原子、チオアミドの窒素原子、ウレアの窒素原子、チオウレアの窒素原子、ウレタンの窒素原子、含窒素へテロ環の窒素原子の隣接位に結合した窒素原子等が挙げられる。従って、特定化合物としては、アミドの窒素原子、チオアミドの窒素原子、ウレアの窒素原子、チオウレアの窒素原子、ウレタンの窒素原子、含窒素へテロ環の窒素原子の隣接位に結合した窒素原子等から選ばれる窒素原子に、メチノール基及びアルコキシメチル基の少なくともいずれかが結合した構造を有する化合物を指す。
なお、Ｎ－アルコキシメチル基（Ｎ－ＣＨ２ＯＲ、ここでＲはアルキル基）におけるアルキル基としては、炭素数１～２０の直鎖状又は分岐状のアルキル基等が挙げられ、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、セチル基又はステアリル基等が挙げられる。これらの中でも、同アルキル基としては、炭素数１～６の直鎖状又は分岐状のアルキル基が好ましい。 <Compound having at least one of N-methylol group and N-alkoxymethyl group>
The N of the N-methylol group and the N-alkoxymethyl group, that is, the nitrogen atom, includes the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, and the nitrogen-containing heterocycle. Examples thereof include nitrogen atoms bonded to adjacent positions of nitrogen atoms. Therefore, the specific compound includes a nitrogen atom of amide, a nitrogen atom of thioamide, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of urethane, a nitrogen atom bonded to an adjacent position of a nitrogen atom of a nitrogen-containing heterocycle, and the like. Refers to a compound having a structure in which at least one of a methinol group and an alkoxymethyl group is bonded to a selected nitrogen atom.
Examples of the alkyl group in the N-alkoxymethyl group (N-CH 2 OR, where R is an alkyl group) include a linear or branched alkyl group having 1 to 20 carbon atoms, and examples thereof include methyl. Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, neopentyl group, tert-pentyl group, hexyl group, heptyl group, Examples thereof include an octyl group, a nonyl group, a decyl group, a cetyl group or a stearyl group. Among these, as the alkyl group, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable.
Ｎ－メチロール基及びＮ－アルコキシメチル基のＮ、すなわち窒素原子としては、アミドの窒素原子、チオアミドの窒素原子、ウレアの窒素原子、チオウレアの窒素原子、ウレタンの窒素原子、含窒素へテロ環の窒素原子の隣接位に結合した窒素原子等が挙げられる。従って、特定化合物としては、アミドの窒素原子、チオアミドの窒素原子、ウレアの窒素原子、チオウレアの窒素原子、ウレタンの窒素原子、含窒素へテロ環の窒素原子の隣接位に結合した窒素原子等から選ばれる窒素原子に、メチノール基及びアルコキシメチル基の少なくともいずれかが結合した構造を有する化合物を指す。
なお、Ｎ－アルコキシメチル基（Ｎ－ＣＨ２ＯＲ、ここでＲはアルキル基）におけるアルキル基としては、炭素数１～２０の直鎖状又は分岐状のアルキル基等が挙げられ、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、セチル基又はステアリル基等が挙げられる。これらの中でも、同アルキル基としては、炭素数１～６の直鎖状又は分岐状のアルキル基が好ましい。 <Compound having at least one of N-methylol group and N-alkoxymethyl group>
The N of the N-methylol group and the N-alkoxymethyl group, that is, the nitrogen atom, includes the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, and the nitrogen-containing heterocycle. Examples thereof include nitrogen atoms bonded to adjacent positions of nitrogen atoms. Therefore, the specific compound includes a nitrogen atom of amide, a nitrogen atom of thioamide, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of urethane, a nitrogen atom bonded to an adjacent position of a nitrogen atom of a nitrogen-containing heterocycle, and the like. Refers to a compound having a structure in which at least one of a methinol group and an alkoxymethyl group is bonded to a selected nitrogen atom.
Examples of the alkyl group in the N-alkoxymethyl group (N-CH 2 OR, where R is an alkyl group) include a linear or branched alkyl group having 1 to 20 carbon atoms, and examples thereof include methyl. Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, neopentyl group, tert-pentyl group, hexyl group, heptyl group, Examples thereof include an octyl group, a nonyl group, a decyl group, a cetyl group or a stearyl group. Among these, as the alkyl group, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable.
特定化合物の具体例としては、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、及びアルコキシメチル化メラミン等の化合物が挙げられる。
Specific examples of the specific compound include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
アルコキシメチル化グリコールウリルの具体例としては、例えば、１，３，４，６－テトラキス（メトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ブトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ヒドロキシメチル）グリコールウリル、１，３－ビス（ヒドロキシメチル）尿素、１，１，３，３－テトラキス（ブトキシメチル）尿素、１，１，３，３－テトラキス（メトキシメチル）尿素、１，３－ビス（ヒドロキシメチル）－４，５－ジヒドロキシ－２－イミダゾリノン及び１，３－ビス（メトキシメチル）－４，５－ジメトキシ－２－イミダゾリノン等が挙げられる。市販品として、日本サイテック・インダストリーズ（株）（旧 三井サイテック（株））製グリコールウリル化合物（商品名：サイメル（登録商標）１１７０、パウダーリンク（登録商標）１１７４）等の化合物、メチル化尿素樹脂（商品名：ＵＦＲ（登録商標）６５）、ブチル化尿素樹脂（商品名：ＵＦＲ（登録商標）３００、Ｕ－ＶＡＮ１０Ｓ６０、Ｕ－ＶＡＮ１０Ｒ、Ｕ－ＶＡＮ１１ＨＶ）、ＤＩＣ（株）（旧 大日本インキ化学工業（株））製尿素／ホルムアルデヒド系樹脂（高縮合型、商品名：ベッカミン（登録商標）Ｊ－３００Ｓ、同Ｐ－９５５、同Ｎ）等が挙げられる。
Specific examples of alkoxymethylated glycol uryl include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycol uryl, 1,3,4,6-tetrakis (butoxymethyl) glycol uryl, 1,3,4. , 6-Tetrax (hydroxymethyl) glycol uryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercial products, compounds such as glycoluril compound (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174) manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.), methylated urea resin (Product name: UFR (registered trademark) 65), Butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Co., Ltd. (formerly Dainippon Ink and Chemicals) Examples thereof include urea / formaldehyde-based resins manufactured by Kogyo Co., Ltd. (highly condensed type, trade name: Beccamin (registered trademark) J-300S, P-955, N) and the like.
アルコキシメチル化ベンゾグアナミンの具体例としてはテトラメトキシメチルベンゾグアナミン等が挙げられる。市販品として、日本サイテック・インダストリーズ（株）（旧 三井サイテック（株））製（商品名：サイメル（登録商標）１１２３）、（株）三和ケミカル製（商品名：ニカラック（登録商標）ＢＸ－４０００、同ＢＸ－３７、同ＢＬ－６０、同ＢＸ－５５Ｈ）等が挙げられる。
Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. As commercial products, Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nicarac (registered trademark) BX- 4000, BX-37, BL-60, BX-55H) and the like.
アルコキシメチル化メラミンの具体例としては、例えば、ヘキサメトキシメチルメラミン等が挙げられる。市販品として、日本サイテック・インダストリーズ（株）（旧 三井サイテック（株））製メトキシメチルタイプメラミン化合物（商品名：サイメル（登録商標）３００、同３０１、同３０３、同３５０）、ブトキシメチルタイプメラミン化合物（商品名：マイコート（登録商標）５０６、同５０８）、（株）三和ケミカル製メトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＷ－３０、同ＭＷ－２２、同ＭＷ－１１、同ＭＳ－００１、同ＭＸ－００２、同ＭＸ－７３０、同ＭＸ－７５０、同ＭＸ－０３５）、ブトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＸ－４５、同ＭＸ－４１０、同ＭＸ－３０２）等が挙げられる。
Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Commercially available products include methoxymethyl type melamine compound manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine. Compounds (trade name: Mycoat (registered trademark) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd. (trade name: Nicarac (registered trademark) MW-30, MW-22, MW- 11, MS-001, MX-002, MX-730, MX-750, MX-035), Butoxymethyl type melamine compound (trade name: Nicarac (registered trademark) MX-45, MX-410) , MX-302) and the like.
また、このようなアミノ基の水素原子がメチロール基又はアルコキシメチル基で置換されたメラミン化合物、尿素化合物、グリコールウリル化合物及びベンゾグアナミン化合物を縮合させて得られる化合物であっても良い。例えば、米国特許第６３２３３１０号に記載されているメラミン化合物及びベンゾグアナミン化合物から製造される高分子量の化合物が挙げられる。上記メラミン化合物の市販品としては、商品名：サイメル（登録商標）３０３等が挙げられ、上記ベンゾグアナミン化合物の市販品としては、商品名：サイメル（登録商標）１１２３（以上、日本サイテック・インダストリーズ（株）（旧 三井サイテック（株））製）等が挙げられる。
Further, it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds produced from the melamine and benzoguanamine compounds described in US Pat. No. 6,323,310. Examples of the commercially available product of the melamine compound include trade name: Cymel (registered trademark) 303 and the like, and the commercially available product of the above benzoguanamine compound includes the product name: Cymel (registered trademark) 1123 (above, Japan Cytec Industries Co., Ltd.). ) (Formerly manufactured by Mitsui Cytec Co., Ltd.).
さらに、特定化合物として、Ｎ－ヒドロキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－エトキシメチルアクリルアミド、Ｎ－ブトキシメチルメタクリルアミド等のメチロール基又はアルコキシメチル基で置換されたアクリルアミド化合物又はメタクリルアミド化合物を使用して製造されるポリマーも用いることができる。
Further, as the specific compound, an acrylamide compound or a methacrylamide compound substituted with a methylol group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylate, N-ethoxymethylacrylamide, N-butoxymethylmethacrylate or the like and an alkoxymethyl group may be used. Polymers produced using it can also be used.
そのようなポリマーとしては、例えば、ポリ（Ｎ－ブトキシメチルアクリルアミド）、Ｎ－ブトキシメチルアクリルアミドとスチレンとの共重合体、Ｎ－ヒドロキシメチルメタクリルアミドとメチルメタクリレートとの共重合体、Ｎ－エトキシメチルメタクリルアミドとベンジルメタクリレートとの共重合体及びＮ－ブトキシメチルアクリルアミドとベンジルメタクリレートと２－ヒドロキシプロピルメタクリレートとの共重合体等が挙げられる。
Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a polymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include a polymer of methacrylamide and benzyl methacrylate, and a polymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
また、そのようなポリマーとして、Ｎ－アルコキシメチル基とＣ＝Ｃ二重結合とを含む重合性基とを有する重合体を用いることも出来る。
Further, as such a polymer, a polymer having a polymerizable group containing an N-alkoxymethyl group and a C = C double bond can also be used.
Ｃ＝Ｃ二重結合を含む重合性基としては、アクリル基、メタクリル基、ビニル基、アリル基、マレイミド基等が挙げられる。
Examples of the polymerizable group containing a C = C double bond include an acrylic group, a methacrylic group, a vinyl group, an allyl group, a maleimide group and the like.
さらに、特定化合物として、ウレタン結合の窒素原子にメチロール基及びアルコキシメチル基の少なくともいずれかが結合した構造を有する化合物も用いることができる。そのような化合物としては、例えば、下記［ＤＭ－１］、［ＤＭ－２］、［ＤＭ－３］、［ＤＭ－４］などが挙げられる。
Further, as a specific compound, a compound having a structure in which at least one of a methylol group and an alkoxymethyl group is bonded to a nitrogen atom of a urethane bond can also be used. Examples of such a compound include the following [DM-1], [DM-2], [DM-3], [DM-4] and the like.
液体組成物中に特定化合物を含有することは、例えば、プロトン核磁気共鳴分光法（１Ｈ－ＮＭＲ）、赤外分光法等により液体組成物を測定することによって確認することができる。
The inclusion of the specific compound in the liquid composition can be confirmed by measuring the liquid composition by, for example, proton nuclear magnetic resonance spectroscopy ( 1 H-NMR), infrared spectroscopy, or the like.
（液体組成物中のホルムアルデヒドを低減する方法及び液体組成物の製造方法）
本発明の方法は、ホルムアルデヒド捕捉剤を、液体組成物に添加する工程を含むことで液体組成物中のホルムアルデヒドを低減する方法及び液体組成物を製造する方法である。
ホルムアルデヒド捕捉剤を液体組成物に添加する方法については特に制限されない。添加する方法としては、例えば、ホルムアルデヒド捕捉剤を液体組成物にそのまま単体で添加する方法、ホルムアルデヒド捕捉剤の溶剤溶液又は懸濁液を液体組成物に添加する方法等があり、組成物の特性や成形体の要求性能に応じて適宜選択すれば良い。また、液体組成物が液体の樹脂組成物である場合には、ホルムアルデヒド捕捉剤を、樹脂組成物の樹脂重合時もしくは重合後、あるいは樹脂成形時の任意の段階で組成物に添加しても良い。さらに、液体の樹脂組成物を、ホルムアルデヒド捕捉剤の溶剤溶液又は懸濁液に添加しても良い。 (Method of reducing formaldehyde in liquid composition and method of manufacturing liquid composition)
The method of the present invention is a method for reducing formaldehyde in a liquid composition and a method for producing a liquid composition by including a step of adding a formaldehyde scavenger to the liquid composition.
The method of adding the formaldehyde scavenger to the liquid composition is not particularly limited. Examples of the method of addition include a method of adding the formaldehyde scavenger to the liquid composition as it is, a method of adding a solvent solution or suspension of the formaldehyde scavenger to the liquid composition, and the like. It may be appropriately selected according to the required performance of the molded body. When the liquid composition is a liquid resin composition, a formaldehyde scavenger may be added to the composition at any stage during or after the resin polymerization of the resin composition or at the time of resin molding. .. Further, the liquid resin composition may be added to the solvent solution or suspension of the formaldehyde scavenger.
本発明の方法は、ホルムアルデヒド捕捉剤を、液体組成物に添加する工程を含むことで液体組成物中のホルムアルデヒドを低減する方法及び液体組成物を製造する方法である。
ホルムアルデヒド捕捉剤を液体組成物に添加する方法については特に制限されない。添加する方法としては、例えば、ホルムアルデヒド捕捉剤を液体組成物にそのまま単体で添加する方法、ホルムアルデヒド捕捉剤の溶剤溶液又は懸濁液を液体組成物に添加する方法等があり、組成物の特性や成形体の要求性能に応じて適宜選択すれば良い。また、液体組成物が液体の樹脂組成物である場合には、ホルムアルデヒド捕捉剤を、樹脂組成物の樹脂重合時もしくは重合後、あるいは樹脂成形時の任意の段階で組成物に添加しても良い。さらに、液体の樹脂組成物を、ホルムアルデヒド捕捉剤の溶剤溶液又は懸濁液に添加しても良い。 (Method of reducing formaldehyde in liquid composition and method of manufacturing liquid composition)
The method of the present invention is a method for reducing formaldehyde in a liquid composition and a method for producing a liquid composition by including a step of adding a formaldehyde scavenger to the liquid composition.
The method of adding the formaldehyde scavenger to the liquid composition is not particularly limited. Examples of the method of addition include a method of adding the formaldehyde scavenger to the liquid composition as it is, a method of adding a solvent solution or suspension of the formaldehyde scavenger to the liquid composition, and the like. It may be appropriately selected according to the required performance of the molded body. When the liquid composition is a liquid resin composition, a formaldehyde scavenger may be added to the composition at any stage during or after the resin polymerization of the resin composition or at the time of resin molding. .. Further, the liquid resin composition may be added to the solvent solution or suspension of the formaldehyde scavenger.
ホルムアルデヒドの濃度を半分以上低減するための捕捉剤の添加量は、使用するホルムアルデヒド捕捉剤の種類によって変わるため、一概に説明することはできない。特に好ましいホルムアルデヒド捕捉剤として挙げた２－アミノエタンチオールや１，８－ジアミノナフタレンにおいては液体組成物中に存在するホルムアルデヒドのモル比５当量以下の添加で大部分のホルムアルデヒドと反応し、ホルムアルデヒドの濃度を７０％から９５％の範囲で低減することができる。２－アミノエタンチオールや１，８－ジアミノナフタレン以外の化合物においても先行特許等で示されてきた化合物より少ない添加量でホルムアルデヒド濃度を低減することができる。従って、ホルムアルデヒド捕捉剤の添加量としては、特に制限されるものではないが、ホルムアルデヒド捕捉剤を添加する前の液体組成物中におけるホルムアルデヒドに対して、０．１モル当量以上が好ましく、０．３モル当量以上がより好ましく、０．５モル当量以上がさらに好ましく、１モル当量以上が特に好ましいい。また、同添加量は、５００モル当量以下が好ましく、１００モル当量以下がより好ましく、２０モル当量以下がさらに好ましく、５モル当量以下が特に好ましい。
The amount of the scavenger added to reduce the formaldehyde concentration by more than half varies depending on the type of formaldehyde scavenger used, so it cannot be explained unconditionally. In 2-aminoethanethiol and 1,8-diaminonaphthalene, which are mentioned as particularly preferable formaldehyde scavengers, the concentration of formaldehyde reacts with most of the formaldehyde when the molar ratio of formaldehyde present in the liquid composition is 5 equivalents or less. Can be reduced in the range of 70% to 95%. Even in compounds other than 2-aminoethanethiol and 1,8-diaminonaphthalene, the formaldehyde concentration can be reduced with a smaller addition amount than the compounds shown in the prior patents and the like. Therefore, the amount of the formaldehyde scavenger added is not particularly limited, but is preferably 0.1 molar equivalent or more with respect to the formaldehyde in the liquid composition before the addition of the formaldehyde scavenger, preferably 0.3. More than a molar equivalent is more preferable, more preferably 0.5 molar equivalent or more, and particularly preferably 1 molar equivalent or more. The addition amount is preferably 500 molar equivalents or less, more preferably 100 molar equivalents or less, further preferably 20 molar equivalents or less, and particularly preferably 5 molar equivalents or less.
ホルムアルデヒド捕捉剤を液体組成物に添加した後、必要に応じて液体組成物を混合しても良い。混合時間は、特に限定されないが、通常５分～３００分であり、５分～１２０分であることが好ましい。また、混合温度は、特に限定されないが、通常５～７０℃であり、５～６０℃であることが好ましい。
After adding the formaldehyde scavenger to the liquid composition, the liquid composition may be mixed if necessary. The mixing time is not particularly limited, but is usually 5 minutes to 300 minutes, preferably 5 minutes to 120 minutes. The mixing temperature is not particularly limited, but is usually 5 to 70 ° C, preferably 5 to 60 ° C.
またホルムアルデヒドを含む液体組成物の機能を損なわない範囲で、さらなる捕捉効果を期待し液体組成物中のホルムアルデヒドよりも大過剰量のホルムアルデヒド捕捉剤を添加しても良い。さらに従来使用されてきたホルムアルデヒド捕捉剤やその他添加剤と併用しても良い。
Further, as long as the function of the liquid composition containing formaldehyde is not impaired, a formaldehyde trapping agent in a larger amount than that of formaldehyde in the liquid composition may be added in anticipation of a further trapping effect. Further, it may be used in combination with a formaldehyde scavenger or other additives that have been conventionally used.
＜その他添加剤＞
本発明の方法におけるホルムアルデヒド捕捉剤は、本発明の効果を損なわない限りにおいて、必要に応じて、シランカップリング剤、界面活性剤、レオロジー調整剤、顔料、染料、保存安定剤、消泡剤、酸化防止剤等の他の添加物と併せて添加しても良い。 <Other additives>
The formaldehyde trapping agent in the method of the present invention may be a silane coupling agent, a surfactant, a rheology adjuster, a pigment, a dye, a storage stabilizer, an antifoaming agent, if necessary, as long as the effect of the present invention is not impaired. It may be added in combination with other additives such as antioxidants.
本発明の方法におけるホルムアルデヒド捕捉剤は、本発明の効果を損なわない限りにおいて、必要に応じて、シランカップリング剤、界面活性剤、レオロジー調整剤、顔料、染料、保存安定剤、消泡剤、酸化防止剤等の他の添加物と併せて添加しても良い。 <Other additives>
The formaldehyde trapping agent in the method of the present invention may be a silane coupling agent, a surfactant, a rheology adjuster, a pigment, a dye, a storage stabilizer, an antifoaming agent, if necessary, as long as the effect of the present invention is not impaired. It may be added in combination with other additives such as antioxidants.
（液体組成物中のホルムアルデヒド濃度の定量方法）
液体組成物中に存在するホルムアルデヒド濃度については、一般的に使用される方法で定量することができる。具体的にはアセチルアセトン法や２，４－ジニトロフェニルヒドラジン法等を使用することができ、またこれらの方法に限定されない。アセチルアセトン法は液中のホルムアルデヒドを以下の式６の反応に従い標識する手法である。反応によってホルムアルデヒド誘導体は波長４１３ｎｍの光を吸収するため、この吸光を適切な手法で計測することによりホルムアルデヒド濃度を間接的に定量できる。例として誘導体化した溶液を１センチ幅のガラスセルに注ぎ、分光光度計によって直接吸光度を測定する手法が挙げられる。 (Method for quantifying formaldehyde concentration in liquid composition)
The concentration of formaldehyde present in the liquid composition can be quantified by commonly used methods. Specifically, the acetylacetone method, the 2,4-dinitrophenylhydrazine method and the like can be used, and the method is not limited to these methods. The acetylacetone method is a method for labeling formaldehyde in a liquid according to the reaction of the following formula 6. Since the formaldehyde derivative absorbs light having a wavelength of 413 nm by the reaction, the formaldehyde concentration can be indirectly quantified by measuring this absorption by an appropriate method. An example is a method in which a derivatized solution is poured into a glass cell having a width of 1 cm and the absorbance is directly measured by a spectrophotometer.
液体組成物中に存在するホルムアルデヒド濃度については、一般的に使用される方法で定量することができる。具体的にはアセチルアセトン法や２，４－ジニトロフェニルヒドラジン法等を使用することができ、またこれらの方法に限定されない。アセチルアセトン法は液中のホルムアルデヒドを以下の式６の反応に従い標識する手法である。反応によってホルムアルデヒド誘導体は波長４１３ｎｍの光を吸収するため、この吸光を適切な手法で計測することによりホルムアルデヒド濃度を間接的に定量できる。例として誘導体化した溶液を１センチ幅のガラスセルに注ぎ、分光光度計によって直接吸光度を測定する手法が挙げられる。 (Method for quantifying formaldehyde concentration in liquid composition)
The concentration of formaldehyde present in the liquid composition can be quantified by commonly used methods. Specifically, the acetylacetone method, the 2,4-dinitrophenylhydrazine method and the like can be used, and the method is not limited to these methods. The acetylacetone method is a method for labeling formaldehyde in a liquid according to the reaction of the following formula 6. Since the formaldehyde derivative absorbs light having a wavelength of 413 nm by the reaction, the formaldehyde concentration can be indirectly quantified by measuring this absorption by an appropriate method. An example is a method in which a derivatized solution is poured into a glass cell having a width of 1 cm and the absorbance is directly measured by a spectrophotometer.
以下、例を挙げて、本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものでない。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実施例１～７及び比較例１～６において、ホルムアルデヒド捕捉剤を用いた液体組成物中のホルムアルデヒド濃度の低減効果の評価を行った。まず、実施例及び比較例におけるホルムアルデヒド濃度の検出方法について説明する。なお、以下の実施例及び比較例中に説明される混合比は特に明示しない限り体積比についてのものである。なお、混合比がｐｐｍ単位で示されている場合は質量比についてのものである。
In Examples 1 to 7 and Comparative Examples 1 to 6, the effect of reducing the formaldehyde concentration in the liquid composition using the formaldehyde scavenger was evaluated. First, a method for detecting the formaldehyde concentration in Examples and Comparative Examples will be described. The mixing ratios described in the following Examples and Comparative Examples are for volume ratios unless otherwise specified. When the mixing ratio is shown in ppm, it is about the mass ratio.
［液体組成物中のホルムアルデヒドの検出］
液体組成物中のホルムアルデヒドはアセチルアセトン法による誘導体化によって検出した。アセチルアセトン法はサンプル溶液を反応液と混合させ以下の式７の反応に従い標識する手法である。本実施例ではアセチルアセトン法の一般的なプロトコルに従い、酢酸アンモニウム１５ｇ、酢酸６００μｌ、及びアセチルアセトン５００μｌをＭｉｌｌｉ－Ｑの超純水で２００ｍｌにメスアップしたものを反応液として使用した。この反応液と、ホルムアルデヒド捕捉剤を添加した液体組成物とを混合し、５０℃で３０分間反応させた後、室温で３０分静置してホルムデヒド誘導体化液を調製した。ホルムアルデヒド誘導体化液中の誘導体化された化合物であるホルムアルデヒド誘導体を検出した。 [Detection of formaldehyde in liquid composition]
Formaldehyde in the liquid composition was detected by derivatization by the acetylacetone method. The acetylacetone method is a method in which a sample solution is mixed with a reaction solution and labeled according to the reaction of the following formula 7. In this example, according to the general protocol of the acetylacetone method, 15 g of ammonium acetate, 600 μl of acetic acid, and 500 μl of acetylacetone were mixed up to 200 ml with Milli-Q ultrapure water and used as a reaction solution. This reaction solution and a liquid composition to which a formaldehyde scavenger was added were mixed, reacted at 50 ° C. for 30 minutes, and then allowed to stand at room temperature for 30 minutes to prepare a formaldehyde derivatized solution. A formaldehyde derivative, which is a derivatized compound, was detected in the formaldehyde derivatizing solution.
液体組成物中のホルムアルデヒドはアセチルアセトン法による誘導体化によって検出した。アセチルアセトン法はサンプル溶液を反応液と混合させ以下の式７の反応に従い標識する手法である。本実施例ではアセチルアセトン法の一般的なプロトコルに従い、酢酸アンモニウム１５ｇ、酢酸６００μｌ、及びアセチルアセトン５００μｌをＭｉｌｌｉ－Ｑの超純水で２００ｍｌにメスアップしたものを反応液として使用した。この反応液と、ホルムアルデヒド捕捉剤を添加した液体組成物とを混合し、５０℃で３０分間反応させた後、室温で３０分静置してホルムデヒド誘導体化液を調製した。ホルムアルデヒド誘導体化液中の誘導体化された化合物であるホルムアルデヒド誘導体を検出した。 [Detection of formaldehyde in liquid composition]
Formaldehyde in the liquid composition was detected by derivatization by the acetylacetone method. The acetylacetone method is a method in which a sample solution is mixed with a reaction solution and labeled according to the reaction of the following formula 7. In this example, according to the general protocol of the acetylacetone method, 15 g of ammonium acetate, 600 μl of acetic acid, and 500 μl of acetylacetone were mixed up to 200 ml with Milli-Q ultrapure water and used as a reaction solution. This reaction solution and a liquid composition to which a formaldehyde scavenger was added were mixed, reacted at 50 ° C. for 30 minutes, and then allowed to stand at room temperature for 30 minutes to prepare a formaldehyde derivatized solution. A formaldehyde derivative, which is a derivatized compound, was detected in the formaldehyde derivatizing solution.
ホルムアルデヒド誘導体は４１３ｎｍの波長の光を吸収するため、この波長の吸光度を測定することで、ホルムアルデヒドを間接的に検出することができる。本実施例では、分光光度計（島津製作所製紫外可視近赤外（ＵＶ－ＶＩＳ－ＮＩＲ）分光光度計ＵＶ－３６００）を使用し、ホルムアルデヒド誘導体化液を１センチセルガラスに入れて４１３ｎｍの吸光度を測定しホルムアルデヒドの減少量を計算した。
Since the formaldehyde derivative absorbs light having a wavelength of 413 nm, formaldehyde can be indirectly detected by measuring the absorbance at this wavelength. In this embodiment, a spectrophotometer (UV-VIS-NIR spectrophotometer UV-3600 manufactured by Shimadzu Corporation) is used, and a formaldehyde derivatizing solution is placed in a 1-centimeter cell glass to have an absorbance at 413 nm. Was measured and the amount of reduction in ultraviolet rays was calculated.
分光光度計を用いた検出では、ホルムアルデヒド溶液の代わりに純水と反応液を混合した溶液をベースラインとした。これにより吸光スペクトルから反応液自体に由来する吸収が除かれるため、ホルムアルデヒド誘導体の吸収を見ることができる。本実施例では純水又は後述するホルムアルデヒド抽出液を１、反応液を９の割合で混合して使用した。
以下の実施例１～７及び比較例１～６は、上述した検出方法により実施した。 For detection using a spectrophotometer, a solution in which pure water and a reaction solution were mixed instead of a formaldehyde solution was used as the baseline. As a result, the absorption derived from the reaction solution itself is removed from the absorption spectrum, so that the absorption of the formaldehyde derivative can be seen. In this example, pure water or a formaldehyde extract described later was mixed at a ratio of 1 and a reaction solution was used at a ratio of 9.
The following Examples 1 to 7 and Comparative Examples 1 to 6 were carried out by the above-mentioned detection method.
以下の実施例１～７及び比較例１～６は、上述した検出方法により実施した。 For detection using a spectrophotometer, a solution in which pure water and a reaction solution were mixed instead of a formaldehyde solution was used as the baseline. As a result, the absorption derived from the reaction solution itself is removed from the absorption spectrum, so that the absorption of the formaldehyde derivative can be seen. In this example, pure water or a formaldehyde extract described later was mixed at a ratio of 1 and a reaction solution was used at a ratio of 9.
The following Examples 1 to 7 and Comparative Examples 1 to 6 were carried out by the above-mentioned detection method.
［水溶液中のホルムアルデヒド低減評価］
＜実施例１、２及び比較例１～３＞
ホルムアルデヒド標品（富士フイルム和光純薬（株）製ホルムアルデヒド０．１％メタノール溶液）を純水によって、ホルムアルデヒド濃度が質量比１０ｐｐｍになるように希釈した。この水溶液に対し、以下の表１の通りに実施例１、２及び比較例１～３のホルムアルデヒド捕捉剤を添加した。次いで、添加後の水溶液中のホルムアルデヒドを検出し、液体組成物である水溶液中のホルムアルデヒド低減効果を評価した。結果を表１に示す。 [Evaluation of formaldehyde reduction in aqueous solution]
<Examples 1 and 2 and Comparative Examples 1 to 3>
The formaldehyde standard (formaldehyde 0.1% methanol solution manufactured by Wako Pure Chemical Industries, Ltd.) was diluted with pure water so that the formaldehyde concentration was 10 ppm by mass. The formaldehyde scavengers of Examples 1 and 2 and Comparative Examples 1 to 3 were added to this aqueous solution as shown in Table 1 below. Next, formaldehyde in the aqueous solution after addition was detected, and the formaldehyde reducing effect in the aqueous solution as a liquid composition was evaluated. The results are shown in Table 1.
＜実施例１、２及び比較例１～３＞
ホルムアルデヒド標品（富士フイルム和光純薬（株）製ホルムアルデヒド０．１％メタノール溶液）を純水によって、ホルムアルデヒド濃度が質量比１０ｐｐｍになるように希釈した。この水溶液に対し、以下の表１の通りに実施例１、２及び比較例１～３のホルムアルデヒド捕捉剤を添加した。次いで、添加後の水溶液中のホルムアルデヒドを検出し、液体組成物である水溶液中のホルムアルデヒド低減効果を評価した。結果を表１に示す。 [Evaluation of formaldehyde reduction in aqueous solution]
<Examples 1 and 2 and Comparative Examples 1 to 3>
The formaldehyde standard (formaldehyde 0.1% methanol solution manufactured by Wako Pure Chemical Industries, Ltd.) was diluted with pure water so that the formaldehyde concentration was 10 ppm by mass. The formaldehyde scavengers of Examples 1 and 2 and Comparative Examples 1 to 3 were added to this aqueous solution as shown in Table 1 below. Next, formaldehyde in the aqueous solution after addition was detected, and the formaldehyde reducing effect in the aqueous solution as a liquid composition was evaluated. The results are shown in Table 1.
表１中の「ホルムアルデヒド検出量比」は、ホルムアルデヒド１０ｐｐｍの標品を誘導体化処理し、分光光度計で検出を行った際の４１３ｎｍにおける吸光度を基準とし、実施例及び比較例のサンプルにおける吸光度の倍数を示したものである。
そのため１，８－ジアミノナフタレンを１００ｐｐｍ添加した、本発明の方法である実施例１の場合には、吸光度は０．４９倍になっており、減少した吸光度分のホルムアルデヒドがホルムアルデヒド捕捉剤と反応、捕捉されているものと考えられる。 The "formaldehyde detection amount ratio" in Table 1 is based on the absorbance at 413 nm when a standard of 10 ppm formaldehyde is derivatized and detected by a spectrophotometer, and the absorbance in the samples of Examples and Comparative Examples is used as a reference. It shows a multiple.
Therefore, in the case of Example 1 in which 100 ppm of 1,8-diaminonaphthalene was added, the absorbance was 0.49 times, and the reduced absorbance of formaldehyde reacted with the formaldehyde scavenger. It is believed that it has been captured.
そのため１，８－ジアミノナフタレンを１００ｐｐｍ添加した、本発明の方法である実施例１の場合には、吸光度は０．４９倍になっており、減少した吸光度分のホルムアルデヒドがホルムアルデヒド捕捉剤と反応、捕捉されているものと考えられる。 The "formaldehyde detection amount ratio" in Table 1 is based on the absorbance at 413 nm when a standard of 10 ppm formaldehyde is derivatized and detected by a spectrophotometer, and the absorbance in the samples of Examples and Comparative Examples is used as a reference. It shows a multiple.
Therefore, in the case of Example 1 in which 100 ppm of 1,8-diaminonaphthalene was added, the absorbance was 0.49 times, and the reduced absorbance of formaldehyde reacted with the formaldehyde scavenger. It is believed that it has been captured.
先行文献（国際公開第２００１／０６２８３８号）では、アセトアルデヒドと高い反応性を有することからポリエステル中のアセトデヒド含有量を低減する最も好ましい化合物としてアントラニルアミドが記載されている。また、先行文献（国際公開第２００５／０４４９１７号）ではホルムアルデヒドと高い反応性を有することからホルムアルデヒド抑制剤としてヒドラジン系化合物が記載されている。しかし、アントラニルアミドを用いた比較例１及びヒドラジン系化合物である４－メチルベンゾヒドラジンを用いた比較例３は、ホルムアルデヒドに対して質量比１００倍もの量を添加しているにも関わらず、一割程度しかホルムアルデヒドが低減されていなかった。これに対して、１，８－ジアミノナフタレンを用いた、本発明の方法である実施例２では、比較例１及び３の添加量の１００分の１量で同程度の低減効果が得られていることから、本発明の方法におけるホルムアルデヒド捕捉剤のホルムアルデヒド捕捉能の高さが示された。また、基Ａ及び基Ｂを備えず、本発明の方法に係るホルムアルデヒド捕捉剤ではないジアミン化合物を用いた比較例２は、ホルムアルデヒド低減効果が低かった。
Prior literature (International Publication No. 2001/062838) describes anthranil amide as the most preferable compound for reducing the acetaldehyde content in polyester because it has high reactivity with acetaldehyde. Further, in the prior art (International Publication No. 2005/0494917), a hydrazine-based compound is described as a formaldehyde inhibitor because it has high reactivity with formaldehyde. However, in Comparative Example 1 using anthranil amide and Comparative Example 3 using 4-methylbenzohydrazine, which is a hydrazine-based compound, even though the amount of formaldehyde added was 100 times the mass ratio, one Formaldehyde was reduced only by a percentage. On the other hand, in Example 2 which is the method of the present invention using 1,8-diaminonaphthalene, the same reduction effect was obtained with 1/100 of the addition amount of Comparative Examples 1 and 3. Therefore, the high formaldehyde scavenging ability of the formaldehyde scavenger in the method of the present invention was shown. Further, Comparative Example 2 using a diamine compound which does not have a group A and a group B and is not a formaldehyde scavenger according to the method of the present invention had a low formaldehyde reducing effect.
［樹脂溶液中のホルムアルデヒド低減評価］
＜実施例３～７及び比較例４～６＞
液体組成物としてホルムアルデヒド１００ｐｐｍを含有する、Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物である、重合物ＰＢＭＡＡ（ポリＮ－ブトキシメチルアクリルアミド）のＰＧＭＥ（プロピレングリコールモノメチルエーテル）溶液を用いて樹脂溶液中のホルムアルデヒド低減効果を評価した。ＰＢＭＡＡのモノマーであるＮ－ＢＭＡＡ（Ｎ－ブトキシメチルアクリルアミド）は先行文献（特許第３９４５８３４号）で示されるように、合成時にホルムアルデヒドを使用し、アクリルアミドにメチロール基を付加している。そのためこの合成時からの持ち込みやブトキシ基及びメチロール基の脱離によってホルムアルデヒドがＰＢＭＡＡ溶液中に存在すると考えられる。 [Evaluation of formaldehyde reduction in resin solution]
<Examples 3 to 7 and Comparative Examples 4 to 6>
A PGME (propylene glycol monomethyl ether) solution of the polymer PBMAA (poly N-butoxymethyl acrylamide), which is a compound having at least one of an N-methylol group and an N-alkoxymethyl group, containing 100 ppm of formaldehyde as a liquid composition. Was used to evaluate the formaldehyde reduction effect in the resin solution. As shown in the prior art (Patent No. 39455834), N-BMAA (N-butoxymethylacrylamide), which is a monomer of PBMAA, uses formaldehyde at the time of synthesis and adds a methylol group to acrylamide. Therefore, it is considered that formaldehyde is present in the PBMAA solution due to the introduction from the time of this synthesis and the elimination of the butoxy group and the methylol group.
＜実施例３～７及び比較例４～６＞
液体組成物としてホルムアルデヒド１００ｐｐｍを含有する、Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物である、重合物ＰＢＭＡＡ（ポリＮ－ブトキシメチルアクリルアミド）のＰＧＭＥ（プロピレングリコールモノメチルエーテル）溶液を用いて樹脂溶液中のホルムアルデヒド低減効果を評価した。ＰＢＭＡＡのモノマーであるＮ－ＢＭＡＡ（Ｎ－ブトキシメチルアクリルアミド）は先行文献（特許第３９４５８３４号）で示されるように、合成時にホルムアルデヒドを使用し、アクリルアミドにメチロール基を付加している。そのためこの合成時からの持ち込みやブトキシ基及びメチロール基の脱離によってホルムアルデヒドがＰＢＭＡＡ溶液中に存在すると考えられる。 [Evaluation of formaldehyde reduction in resin solution]
<Examples 3 to 7 and Comparative Examples 4 to 6>
A PGME (propylene glycol monomethyl ether) solution of the polymer PBMAA (poly N-butoxymethyl acrylamide), which is a compound having at least one of an N-methylol group and an N-alkoxymethyl group, containing 100 ppm of formaldehyde as a liquid composition. Was used to evaluate the formaldehyde reduction effect in the resin solution. As shown in the prior art (Patent No. 39455834), N-BMAA (N-butoxymethylacrylamide), which is a monomer of PBMAA, uses formaldehyde at the time of synthesis and adds a methylol group to acrylamide. Therefore, it is considered that formaldehyde is present in the PBMAA solution due to the introduction from the time of this synthesis and the elimination of the butoxy group and the methylol group.
ＰＢＭＡＡのＰＧＭＥ溶液中のホルムアルデヒド検出は、水と樹脂溶液を混合させ遠心分離を行った後、上澄みの水層を回収し、これをホルムアルデヒド抽出液として使用した。ＰＢＭＡＡは水に不溶であることから遠心分離によって底部に沈殿し、ＰＧＭＥ及びホルムアルデヒドのみが水層へと移行する。この樹脂溶液に対して以下の表２の通りに実施例３～７及び比較例４～６のホルムアルデヒド捕捉剤を添加した。次いで、樹脂溶液１、水９の割合で混合し遠心分離（１分間に１００００回転、室温、５分間）後、上層の水層を回収することでホルムアルデヒド抽出液を得た。得られたホルムアルデヒド抽出液中のホルムアルデヒドを検出し、樹脂溶液中のホルムアルデヒド低減効果を評価した。結果を表２に示す。
For formaldehyde detection in the PGME solution of PBMAA, water and a resin solution were mixed and centrifuged, and then the aqueous layer of the supernatant was recovered and used as a formaldehyde extract. Since PBMAA is insoluble in water, it precipitates at the bottom by centrifugation, and only PGME and formaldehyde are transferred to the aqueous layer. The formaldehyde scavengers of Examples 3 to 7 and Comparative Examples 4 to 6 were added to this resin solution as shown in Table 2 below. Then, the resin solution 1 and water 9 were mixed and centrifuged (10000 rpm, room temperature, 5 minutes), and then the upper aqueous layer was recovered to obtain a formaldehyde extract. Formaldehyde in the obtained formaldehyde extract was detected, and the formaldehyde reduction effect in the resin solution was evaluated. The results are shown in Table 2.
表２中の「ホルムアルデヒド検出量比」はホルムアルデヒド捕捉剤を添加していないＰＢＭＡＡ溶液から得たホルムアルデヒド抽出液を誘導体化処理し、分光光度計で検出を行った際の４１３ｎｍにおける吸光度を基準としている。本発明の方法である実施例３～７のホルムアルデヒド捕捉剤を添加した場合には、ホルムアルデヒドの検出量を数十％、特に実施例３の１，８－ジアミノナフタレン及び実施例６の２－アミノエタンチオールを添加した場合には、検出量を７０％以上低減することに成功した。一方、先行文献（特開２０２０－０２２９９６号公報、特開２００４－３５２９２４号公報）においてホルムアルデヒドの検出量を低減する効果があると示されていた比較例４～６のホルムアルデヒド捕捉剤では、実施例３～７のホルムアルデヒド捕捉剤よりも大量に添加したがそれ以上の低減効果は見られなかった。これは実施例３～７のホルムアルデヒド捕捉剤がホルムアルデヒドと反応するとき５員環又は６員環を形成し、安定な構造を形成し得るためであると考えられる。
The "formaldehyde detection amount ratio" in Table 2 is based on the absorbance at 413 nm when the formaldehyde extract obtained from the PBMAA solution to which the formaldehyde scavenger is not added is derivatized and detected by a spectrophotometer. .. When the formaldehyde scavengers of Examples 3 to 7, which are the methods of the present invention, were added, the amount of formaldehyde detected was several tens of percent, particularly 1,8-diaminonaphthalene of Example 3 and 2-amino of Example 6. When ethanethiol was added, the detected amount was successfully reduced by 70% or more. On the other hand, the formaldehyde scavengers of Comparative Examples 4 to 6 shown to have the effect of reducing the amount of formaldehyde detected in the prior arts (Japanese Patent Laid-Open Nos. 2020-022996 and 2004-352924) are Examples. Although it was added in a larger amount than the formaldehyde scavengers of 3 to 7, no further reduction effect was observed. It is considered that this is because the formaldehyde scavengers of Examples 3 to 7 form a 5-membered ring or a 6-membered ring when they react with formaldehyde, and can form a stable structure.
以上の結果から液体組成物中に存在するホルムアルデヒドを低減する方法として、芳香族アミノ基及びメルカプト基から選ばれる基Ａを有するとともに、芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基Ｂを有し、ホルムアルデヒドと上記基Ａと上記基Ｂとが反応することにより５員環又は６員環を形成する化合物が有用であることが示された。
From the above results, as a method for reducing the formaldehyde present in the liquid composition, it has a group A selected from an aromatic amino group and a mercapto group, and is substituted with an aromatic amino group, an aliphatic amino group and a protective group. It has been shown that a compound having a group B selected from an amino group, a hydroxy group and a mercapto group and forming a 5-membered ring or a 6-membered ring by reacting formaldehyde with the above group A and the above group B is useful. Was done.
From the above results, as a method for reducing the formaldehyde present in the liquid composition, it has a group A selected from an aromatic amino group and a mercapto group, and is substituted with an aromatic amino group, an aliphatic amino group and a protective group. It has been shown that a compound having a group B selected from an amino group, a hydroxy group and a mercapto group and forming a 5-membered ring or a 6-membered ring by reacting formaldehyde with the above group A and the above group B is useful. Was done.
Claims (16)
- ホルムアルデヒド捕捉剤を液体組成物に添加する工程を含む、液体組成物中のホルムアルデヒドを低減する方法であって、
前記ホルムアルデヒド捕捉剤は、芳香族アミノ基及びメルカプト基から選ばれる基Ａを有するとともに、芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基Ｂを有し、ホルムアルデヒドと前記基Ａと前記基Ｂとが反応することにより５員環又は６員環を形成する化合物である、
液体組成物中のホルムアルデヒドを低減する方法。 A method of reducing formaldehyde in a liquid composition, comprising the step of adding a formaldehyde scavenger to the liquid composition.
The formaldehyde scavenger has a group A selected from an aromatic amino group and a mercapto group, and is a group selected from an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group. A compound having B and forming a 5-membered ring or a 6-membered ring by reacting formaldehyde with the group A and the group B.
A method of reducing formaldehyde in a liquid composition. - 前記液体組成物が、Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物を含有する液体組成物である、請求項１に記載の液体組成物中のホルムアルデヒドを低減する方法。 The method for reducing formaldehyde in the liquid composition according to claim 1, wherein the liquid composition is a liquid composition containing a compound having at least one of an N-methylol group and an N-alkoxymethyl group.
- 前記基Ｂが、芳香族アミノ基、脂肪族アミノ基及びメルカプト基から選ばれる、請求項１又は２に記載の液体組成物中のホルムアルデヒドを低減する方法。 The method for reducing formaldehyde in the liquid composition according to claim 1 or 2, wherein the group B is selected from an aromatic amino group, an aliphatic amino group and a mercapto group.
- 前記ホルムアルデヒド捕捉剤は、２－メルカプトエタノール、２－アミノエタンチオール、１，２－ジチオエタン、３－メルカプトプロパノール、１－アミノ－３－メルカプトプロパン、１，３－ジチオプロパン、α－チオグリセロール、ジメルカプロール、ジメルカプトペンタエリストール、トリメルカプトペンタエリストール、テトラメルカプトペンタエリストール、トリメルカプトトリメチロールプロパン、ＤＬ－ジチオトレイトール、Ｌ－システイン、Ｎ－アセチル－Ｌ－システイン、２，３－ジアミノピリジン、３，４－ジアミノ安息香酸及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、請求項１又は２に記載の液体組成物中のホルムアルデヒドを低減する方法。 The formaldehyde trapping agent is 2-mercaptoethanol, 2-aminoethanethiol, 1,2-dithioethane, 3-mercaptopropanol, 1-amino-3-mercaptopropane, 1,3-dithiopropane, α-thioglycerol, di Mercaprol, Dimercaptopentaesterol, Trimercaptopentaeristol, Tetramercaptopentaeristol, Trimercaptotrimethylol Propane, DL-dithiothreitol, L-cysteine, N-acetyl-L-cysteine, 2,3-diamino The method for reducing formaldehyde in the liquid composition according to claim 1 or 2, which is at least one compound selected from the group consisting of pyridine, 3,4-diaminobenzoic acid and 1,8-diaminonaphthalene.
- 前記ホルムアルデヒド捕捉剤は、２－アミノエタンチオール、α－チオグリセロール、ＤＬ－ジチオトレイトール、Ｎ－アセチル－Ｌ－システイン及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、請求項４に記載の液体組成物中のホルムアルデヒドを低減する方法。 The formaldehyde scavenger is at least one compound selected from the group consisting of 2-aminoethanethiol, α-thioglycerol, DL-dithiothreitol, N-acetyl-L-cysteine and 1,8-diaminonaphthalene. , The method for reducing formaldehyde in the liquid composition according to claim 4.
- 前記添加する工程における前記ホルムアルデヒド捕捉剤の添加量は、前記ホルムアルデヒド捕捉剤を添加する前の前記液体組成物中におけるホルムアルデヒドに対して、２０モル当量以下である、請求項１～５のいずれか一項に記載の液体組成物中のホルムアルデヒドを低減する方法。 One of claims 1 to 5, wherein the amount of the formaldehyde scavenger added in the step of adding is 20 mol equivalent or less with respect to the formaldehyde in the liquid composition before the addition of the formaldehyde scavenger. A method for reducing formaldehyde in the liquid composition according to the section.
- 前記Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物は、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、アルコキシメチル化メラミン、Ｎ－メチロール基又はＮ－アルコキシメチル基で置換されたアクリルアミド化合物もしくはメタクリルアミド化合物を使用して製造されるポリマー並びにウレタン結合の窒素原子にメチロール基及びアルコキシメチル基の少なくともいずれかが結合した構造を有する化合物からなる群から選択される少なくとも一種の化合物である、請求項２～６のいずれか一項に記載の液体組成物中のホルムアルデヒドを低減する方法。 The compound having at least one of the N-methylol group and the N-alkoxymethyl group was replaced with an alkoxymethylated glycol uryl, an alkoxymethylated benzoguanamine, an alkoxymethylated melamine, an N-methylol group or an N-alkoxymethyl group. At least one compound selected from the group consisting of a polymer produced using an acrylamide compound or a methacrylamide compound and a compound having a structure in which at least one of a methylol group and an alkoxymethyl group is bonded to a nitrogen atom of a urethane bond. A method for reducing formaldehyde in the liquid composition according to any one of claims 2 to 6.
- 前記液体組成物は、電子デバイス用の液体の樹脂組成物である、請求項１～７のいずれか一項に記載の組成物中のホルムアルデヒドを低減する方法。 The method for reducing formaldehyde in the composition according to any one of claims 1 to 7, wherein the liquid composition is a liquid resin composition for an electronic device.
- ホルムアルデヒド捕捉剤を液体組成物に添加する工程を含む、液体組成物の製造方法であって、
前記ホルムアルデヒド捕捉剤は、芳香族アミノ基及びメルカプト基から選ばれる基Ａを有するとともに、芳香族アミノ基、脂肪族アミノ基、保護基で置換されたアミノ基、ヒドロキシ基及びメルカプト基から選ばれる基Ｂを有し、ホルムアルデヒドと前記基Ａと前記基Ｂとが反応することにより５員環又は６員環を形成する化合物である、
液体組成物の製造方法。 A method for producing a liquid composition, which comprises a step of adding a formaldehyde scavenger to the liquid composition.
The formaldehyde scavenger has a group A selected from an aromatic amino group and a mercapto group, and is a group selected from an aromatic amino group, an aliphatic amino group, an amino group substituted with a protective group, a hydroxy group and a mercapto group. A compound having B and forming a 5-membered ring or a 6-membered ring by reacting formaldehyde with the group A and the group B.
A method for producing a liquid composition. - 前記液体組成物が、Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物を含有する液体組成物である、請求項９に記載の液体組成物の製造方法。 The method for producing a liquid composition according to claim 9, wherein the liquid composition is a liquid composition containing a compound having at least one of an N-methylol group and an N-alkoxymethyl group.
- 前記基Ｂが、芳香族アミノ基、脂肪族アミノ基及びメルカプト基から選ばれる、請求項９又は１０に記載の液体組成物の製造方法。 The method for producing a liquid composition according to claim 9 or 10, wherein the group B is selected from an aromatic amino group, an aliphatic amino group and a mercapto group.
- 前記ホルムアルデヒド捕捉剤は、２－メルカプトエタノール、２－アミノエタンチオール、１，２－ジチオエタン、３－メルカプトプロパノール、１－アミノ－３－メルカプトプロパン、１，３－ジチオプロパン、α－チオグリセロール、ジメルカプロール、ジメルカプトペンタエリストール、トリメルカプトペンタエリストール、テトラメルカプトペンタエリストール、トリメルカプトトリメチロールプロパン、ＤＬ－ジチオトレイトール、Ｌ－システイン、Ｎ－アセチル－Ｌ－システイン、２，３－ジアミノピリジン、３，４－ジアミノ安息香酸及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、請求項９又は１０に記載の液体組成物の製造方法。 The formaldehyde trapping agent is 2-mercaptoethanol, 2-aminoethanethiol, 1,2-dithioethane, 3-mercaptopropanol, 1-amino-3-mercaptopropane, 1,3-dithiopropane, α-thioglycerol, di Mercaprol, Dimercaptopentaesterol, Trimercaptopentaeristol, Tetramercaptopentaeristol, Trimercaptotrimethylol Propane, DL-dithiothreitol, L-cysteine, N-acetyl-L-cysteine, 2,3-diamino The method for producing a liquid composition according to claim 9 or 10, which is at least one compound selected from the group consisting of pyridine, 3,4-diaminobenzoic acid and 1,8-diaminonaphthalene.
- 前記ホルムアルデヒド捕捉剤は、２－アミノエタンチオール、α－チオグリセロール、ＤＬ－ジチオトレイトール、Ｎ－アセチル－Ｌ－システイン及び１，８－ジアミノナフタレンからなる群から選択される少なくとも一種の化合物である、請求項１２に記載の液体組成物の製造方法。 The formaldehyde scavenger is at least one compound selected from the group consisting of 2-aminoethanethiol, α-thioglycerol, DL-dithiothreitol, N-acetyl-L-cysteine and 1,8-diaminonaphthalene. The method for producing a liquid composition according to claim 12.
- 前記添加する工程における前記ホルムアルデヒド捕捉剤の添加量は、前記ホルムアルデヒド捕捉剤を添加する前の前記液体組成物中におけるホルムアルデヒドに対して、２０モル当量以下である、請求項９～１３のいずれか一項に記載の液体組成物の製造方法。 One of claims 9 to 13, wherein the amount of the formaldehyde scavenger added in the step of adding is 20 mol equivalent or less with respect to the formaldehyde in the liquid composition before the addition of the formaldehyde scavenger. The method for producing a liquid composition according to a section.
- 前記Ｎ－メチロール基及びＮ－アルコキシメチル基の少なくともいずれかを有する化合物は、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、アルコキシメチル化メラミン、Ｎ－メチロール基又はＮ－アルコキシメチル基で置換されたアクリルアミド化合物もしくはメタクリルアミド化合物を使用して製造されるポリマー並びにウレタン結合の窒素原子にメチロール基及びアルコキシメチル基の少なくともいずれかが結合した構造を有する化合物からなる群から選択される少なくとも一種の化合物である、請求項１０～１４のいずれか一項に記載の液体組成物の製造方法。 The compound having at least one of the N-methylol group and the N-alkoxymethyl group was replaced with an alkoxymethylated glycol uryl, an alkoxymethylated benzoguanamine, an alkoxymethylated melamine, an N-methylol group or an N-alkoxymethyl group. At least one compound selected from the group consisting of a polymer produced using an acrylamide compound or a methacrylamide compound and a compound having a structure in which at least one of a methylol group and an alkoxymethyl group is bonded to a nitrogen atom of a urethane bond. The method for producing a liquid composition according to any one of claims 10 to 14.
- 前記液体組成物は、電子デバイス用の液体の樹脂組成物である、請求項９～１５のいずれか一項に記載の液体組成物の製造方法。 The method for producing a liquid composition according to any one of claims 9 to 15, wherein the liquid composition is a liquid resin composition for an electronic device.
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| TW202233738A (en) | 2022-09-01 |
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