JP4256467B2 - Formaldehyde scavenger and method for producing the same - Google Patents
Formaldehyde scavenger and method for producing the same Download PDFInfo
- Publication number
- JP4256467B2 JP4256467B2 JP2008533800A JP2008533800A JP4256467B2 JP 4256467 B2 JP4256467 B2 JP 4256467B2 JP 2008533800 A JP2008533800 A JP 2008533800A JP 2008533800 A JP2008533800 A JP 2008533800A JP 4256467 B2 JP4256467 B2 JP 4256467B2
- Authority
- JP
- Japan
- Prior art keywords
- formaldehyde
- urea
- hydrazide compound
- formaldehyde scavenger
- hydrazide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims description 468
- 239000002516 radical scavenger Substances 0.000 title claims description 88
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 100
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 49
- 239000004202 carbamide Substances 0.000 claims description 49
- 150000003672 ureas Chemical class 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 24
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 230000009471 action Effects 0.000 claims description 15
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical group O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims 2
- 239000004566 building material Substances 0.000 description 41
- 230000002000 scavenging effect Effects 0.000 description 31
- 150000001299 aldehydes Chemical class 0.000 description 28
- 239000004480 active ingredient Substances 0.000 description 12
- 238000005507 spraying Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000011491 glass wool Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000004027 organic amino compounds Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000003230 hygroscopic agent Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- KJASTBCNGFYKSR-UHFFFAOYSA-N prop-2-enehydrazide Chemical compound NNC(=O)C=C KJASTBCNGFYKSR-UHFFFAOYSA-N 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- -1 impregnation Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
-
- 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
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2067—Urea
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
Description
本発明は、建材から放出されるホルムアルデヒドを効率的に低減させることができるホルムアルデヒド捕捉剤及びその製造方法に関する。 The present invention relates to a formaldehyde scavenger capable of efficiently reducing formaldehyde released from building materials and a method for producing the same.
近年、住宅等に使用される建材から継続的に室内に発散される化学物質が、人の健康に悪影響を及ぼす事例が多数報告され、大きな社会問題となっている。こうした化学物質の中でも、無色で強い刺激臭のある揮発性有機化合物であるホルムアルデヒドは、安価であるため、合板、パーチクルボードなどの木質系建材又はグラスウールなどの繊維系建材といった建材に、接着剤、塗料、防腐剤等の成分として広く用いられている。ホルムアルデヒドは、建材から空気中に放出された場合には低濃度でも人体に悪影響を及ぼす、いわゆる「シックハウス症候群」の原因物質の一つであることが既に知られている。ホルムアルデヒドは、数ある揮発性有機化合物の中でも、シックハウス問題における優先的取組みの対象になっている。 In recent years, many cases have been reported in which chemical substances continuously emitted from building materials used in houses and the like have an adverse effect on human health, which has become a major social problem. Among these chemical substances, formaldehyde, which is a volatile organic compound that is colorless and has a strong pungent odor, is inexpensive, so it can be used for building materials such as wood-based building materials such as plywood and particle board or fiber-based building materials such as glass wool. Widely used as a preservative component. It is already known that formaldehyde is one of the causative substances of so-called “sick house syndrome” that, when released from building materials into the air, adversely affects the human body even at low concentrations. Formaldehyde is the subject of priority efforts in the sick house problem among other volatile organic compounds.
建材から放出されるホルムアルデヒドの量を減少させる方法として、アジピン酸ジヒドラジドなどのヒドラジド化合物又は尿素若しくはエチレン尿素などの尿素誘導体などといったホルムアルデヒド捕捉効果を有する物質を含む捕捉剤を、例えば接着剤として用いられる樹脂に予め混合するか又は建材に塗布する方法が知られている。アジピン酸ジヒドラジドなどのヒドラジド化合物又は尿素若しくはエチレン尿素などの尿素誘導体は、これらに含まれるＮＨ基がホルムアルデヒドと反応することによって、ホルムアルデヒドを捕捉する。 As a method for reducing the amount of formaldehyde released from building materials, a scavenger containing a substance having a formaldehyde scavenging effect such as a hydrazide compound such as adipic acid dihydrazide or a urea derivative such as urea or ethylene urea is used as an adhesive, for example. Methods are known that are premixed in resin or applied to building materials. Hydrazide compounds such as adipic acid dihydrazide or urea derivatives such as urea or ethylene urea capture formaldehyde by reacting NH groups contained therein with formaldehyde.
しかしながら、尿素又はエチレン尿素などの尿素誘導体は、単独ではホルムアルデヒド捕捉性能が十分ではない。さらに、尿素又はエチレン尿素などの尿素誘導体は、吸湿性が高く、これらを主成分とするホルムアルデヒド捕捉剤を建材に用いた場合には、その建材の周辺材のかびや結露の問題が生じることがある。こういった問題に対処するには、尿素又はエチレン尿素等の尿素誘導体の使用量を少なくする必要があるが、その場合はホルムアルデヒド捕捉効果がさらに低減することになる。一方、アジピン酸ジヒドラジド等のヒドラジド化合物は、尿素等と比較するとホルムアルデヒド捕捉性能が高く吸湿性がないため、周辺材のかびや結露の問題が生じにくいという利点がある。 However, urea derivatives such as urea or ethyleneurea alone do not have sufficient formaldehyde scavenging performance. Furthermore, urea derivatives such as urea or ethylene urea have high hygroscopicity, and when a formaldehyde scavenger containing these as a main component is used as a building material, there may be a problem of mold or condensation on the surrounding material of the building material. . In order to cope with these problems, it is necessary to reduce the use amount of urea or urea derivatives such as ethylene urea. In this case, the formaldehyde scavenging effect is further reduced. On the other hand, a hydrazide compound such as adipic acid dihydrazide has an advantage in that the problem of mold and dew condensation in peripheral materials hardly occurs because it has higher formaldehyde scavenging performance and no hygroscopicity than urea or the like.
アジピン酸ジヒドラジド等のヒドラジド化合物、及び／又は、尿素若しくはエチレン尿素等の尿素誘導体を成分とするホルムアルデヒド捕捉剤に関する先行文献として、以下のものが存在する。
特許文献１は、ヒドラジド類と、尿素及びその誘導体から選ばれる少なくとも１種とを有効成分として含有するホルムアルデヒド消臭剤組成物について開示する。ヒドラジド類を有効成分とする消臭剤が良好なホルムアルデヒド吸着性能を示すこと、及び、尿素やエチレン尿素等の尿素誘導体がホルムアルデヒド吸着能を有することが既に知られていることを前提として、ヒドラジド類と尿素類等とを併用することにより、それぞれを単独で使用した場合と比べて消臭効果が高くなることが開示されている。The followings exist as prior literature relating to formaldehyde scavengers containing hydrazide compounds such as adipic acid dihydrazide and / or urea derivatives such as urea or ethylene urea as components.
Patent Document 1 discloses a formaldehyde deodorant composition containing hydrazides and at least one selected from urea and derivatives thereof as active ingredients. Assuming that deodorants containing hydrazides as active ingredients exhibit good formaldehyde adsorption performance, and that urea derivatives such as urea and ethylene urea have already been known to have formaldehyde adsorption ability, hydrazides It is disclosed that the combined use of urea and urea improves the deodorizing effect compared to the case where each is used alone.
特許文献２は、アクリル酸ヒドラジド系高分子化合物と、酸ヒドラジド系化合物と、尿素及びエチレン尿素を含む有機アミノ化合物の１種又は２種との水溶液を用いて、ホルマリンを除去する技術について開示する。この特許文献２においては、従来、ホルマリンと反応しやすい尿素、エチレン尿素などの有機アミノ化合物を用いてホルマリンを除去することが知られているが、この従来方法は、有機アミノ化合物のホルマリン吸着能が不十分であるためホルマリンの除去が十分に行えないことが示されている。また、この文献においては、ヒドラジド基を含むアクリル酸ヒドラジド系高分子化合物もホルマリンと反応することが知られていることが示されている。 Patent Document 2 discloses a technique for removing formalin using an aqueous solution of an acrylic acid hydrazide polymer compound, an acid hydrazide compound, and one or two organic amino compounds including urea and ethylene urea. . In Patent Document 2, it is conventionally known to remove formalin by using an organic amino compound such as urea or ethylene urea that easily reacts with formalin. However, this conventional method is based on the ability of organic amino compounds to adsorb formalin. It has been shown that formalin cannot be sufficiently removed due to insufficient water content. This document also shows that acrylic hydrazide polymer compounds containing a hydrazide group are known to react with formalin.
特許文献３は、尿素又はその誘導体と、ヒドラジン又はその誘導体と、非揮発性アミン、酸アミド、低級酸の塩及び還元糖類からなる群から選ばれる少なくとも１種と、浸透剤とを含むホルムアルデヒド捕捉剤について開示する。ヒドラジンの誘導体は、少なくともアジピン酸ジヒドラジドを含む。この特許文献３においては、尿素又はその誘導体、及び、ヒドラジン又はその誘導体の含有量が少ない場合には、ホルムアルデヒド捕捉効果が不十分であることが記載されていることから、これらの物質がホルムアルデヒド捕捉性能を有することが示されていると言える。 Patent Document 3 discloses formaldehyde trapping comprising urea or a derivative thereof, hydrazine or a derivative thereof, at least one selected from the group consisting of a non-volatile amine, an acid amide, a salt of a lower acid, and a reducing saccharide, and a penetrant. An agent is disclosed. The derivative of hydrazine contains at least adipic acid dihydrazide. In this Patent Document 3, it is described that when the content of urea or its derivative and hydrazine or its derivative is low, the formaldehyde scavenging effect is insufficient. It can be said that it has been shown to have performance.
特許文献４は、１種又は２種以上のホルムアルデヒド捕捉剤と水性ラテックスからなるホルムアルデヒド捕捉用水性ラテックス組成物について開示する。ホルムアルデヒド捕捉剤として、アミド基を含有する化合物、例えば尿素及び尿素誘導体と、ヒドラジド基を有する化合物、例えばアジピン酸ジヒドラジドが開示されている。 Patent Document 4 discloses an aqueous latex composition for capturing formaldehyde comprising one or more formaldehyde scavengers and an aqueous latex. As formaldehyde scavengers, compounds containing amide groups such as urea and urea derivatives and compounds having hydrazide groups such as adipic acid dihydrazide are disclosed.
以上の各文献から、ヒドラジド化合物並びに尿素及び尿素誘導体を、それぞれ単独で、又は組み合わせて、ホルムアルデヒド捕捉剤として使用することは周知である。 From each of the above documents, it is well known that hydrazide compounds and urea and urea derivatives are used alone or in combination as formaldehyde scavengers.
上記のとおり、アジピン酸ジヒドラジド等のヒドラジド化合物は、吸湿性がなくホルムアルデヒド捕捉効果が高いため、建材に使用されるホルムアルデヒド捕捉剤の有効成分として適しているといえる。しかしながら、アジピン酸ジヒドラジド等のヒドラジド化合物を成分とする捕捉剤における課題の１つとして、ヒドラジド化合物の溶解度が低いという問題がある。アジピン酸ジヒドラジド等のヒドラジド化合物を有効成分とするホルムアルデヒド捕捉剤は、含まれるヒドラジド化合物の量が多いほど、すなわちヒドラジド化合物の濃度が高いほど、ホルムアルデヒド捕捉効果が増大する。しかしながら、ヒドラジド化合物は水に対する溶解度が低いため、濃度を高くすると、含まれるヒドラジド化合物が結晶として析出することがある。したがって、従来、ヒドラジド化合物を高濃度に含むホルムアルデヒド捕捉効果の高いホルムアルデヒド捕捉剤の製造は難しかった。 As described above, hydrazide compounds such as adipic acid dihydrazide are suitable as an active ingredient of a formaldehyde scavenger used for building materials because they are not hygroscopic and have a high formaldehyde scavenging effect. However, as one of the problems with a scavenger containing a hydrazide compound such as adipic acid dihydrazide, there is a problem that the solubility of the hydrazide compound is low. A formaldehyde scavenger containing a hydrazide compound such as adipic acid dihydrazide as an active ingredient increases the formaldehyde scavenging effect as the amount of the hydrazide compound contained, that is, as the concentration of the hydrazide compound increases. However, since the hydrazide compound has low solubility in water, the contained hydrazide compound may precipitate as crystals when the concentration is increased. Therefore, it has been difficult to produce a formaldehyde scavenger having a high formaldehyde scavenging effect and containing a hydrazide compound at a high concentration.
特に、低温環境下では、ヒドラジド化合物の水に対する溶解度が大きく低下する。したがって、アジピン酸ジヒドラジド等のヒドラジド化合物を有効成分とするホルムアルデヒド捕捉剤を含浸、塗布、又は吹き付けた建材の製造工程において、含浸、塗布、又は吹き付け後に建材が低温環境に晒されると、建材の表面や内部にヒドラジド化合物の結晶が析出する。発明者らの行った実験によると、全体を１００重量部とした場合に、アジピン酸ジヒドラジド１２重量部と水８８重量部と含む水溶液について、温度が約１５℃のときにアジピン酸ジヒドラジドが結晶として析出し始めることが分かっている。製造工程において建材に結晶が析出すると、その建材は廃棄しなければならない。しかしながら、アジピン酸ジヒドラジド等のヒドラジド化合物は、他の捕捉剤成分と比べて高価である。したがって、結晶が析出して廃棄される建材が多くなると、生産性が低下すると共に建材製造コストが上昇し、製品価格に影響を与えることになる。製造工程において低温状態が発生しないように製造施設の温度環境を改善することも考えられるが、この場合にはさらに製造コストが上昇する。 In particular, under a low temperature environment, the solubility of the hydrazide compound in water is greatly reduced. Therefore, in the manufacturing process of a building material impregnated, coated, or sprayed with a formaldehyde scavenger containing an hydrazide compound such as adipic acid dihydrazide as an active ingredient, if the building material is exposed to a low temperature environment after impregnation, coating, or spraying, the surface of the building material Crystals of the hydrazide compound are precipitated inside. According to experiments conducted by the inventors, when the total amount is 100 parts by weight, an aqueous solution containing 12 parts by weight of adipic acid dihydrazide and 88 parts by weight of water has adipic acid dihydrazide as crystals when the temperature is about 15 ° C. It is known to begin to precipitate. When crystals are deposited on building materials in the manufacturing process, the building materials must be discarded. However, hydrazide compounds such as adipic acid dihydrazide are more expensive than other scavenger components. Therefore, if the amount of building materials deposited due to the precipitation of crystals increases, the productivity decreases and the building material manufacturing cost increases, which affects the product price. Although it is conceivable to improve the temperature environment of the manufacturing facility so that a low temperature state does not occur in the manufacturing process, in this case, the manufacturing cost further increases.
また、ホルムアルデヒド捕捉剤を含浸、塗布、又は吹き付けた建材の製造工程において、含浸、塗布、又は吹き付け前にホルムアルデヒド捕捉剤を貯蔵しておくことが必要な場合がある。低温の貯蔵環境に置かれた場合には、ホルムアルデヒド捕捉剤に含まれるヒドラジド化合物が析出することがあり、その結果、異なる貯蔵環境に置かれたホルムアルデヒド捕捉剤間で濃度が不均一になる。そうすると、ホルムアルデヒド捕捉剤を建材に使用したときに、有効成分（すなわちヒドラジド化合物）の実使用量が変化し、建材の品質を一定に保つことが困難になる可能性がある。さらに、ホルムアルデヒド捕捉剤は建材に吹き付けて使用することが多いが、吹き付けの際、スプレーノズルを通過するホルムアルデヒド捕捉剤が冷却され、ヒドラジド化合物が析出してノズルの目詰まりを起こす可能性がある。ノズルが目詰まりすると、建材へのホルムアルデヒド捕捉剤の吹き付け量が変化することになる。さらに、ノズルを頻繁に洗浄又は交換することが必要になるため、生産性が低下する。 Further, in the manufacturing process of building materials impregnated, coated or sprayed with formaldehyde scavenger, it may be necessary to store the formaldehyde scavenger before impregnation, coating or spraying. When placed in a low temperature storage environment, the hydrazide compound contained in the formaldehyde scavenger may precipitate, resulting in a non-uniform concentration between formaldehyde scavengers in different storage environments. Then, when the formaldehyde scavenger is used for building materials, the actual usage amount of the active ingredient (that is, hydrazide compound) changes, and it may be difficult to keep the quality of the building materials constant. In addition, the formaldehyde scavenger is often used by spraying on building materials, but during the spraying, the formaldehyde scavenger passing through the spray nozzle is cooled, and the hydrazide compound may precipitate to cause clogging of the nozzle. When the nozzle is clogged, the amount of formaldehyde scavenger sprayed on the building material changes. Furthermore, since it is necessary to frequently clean or replace the nozzle, productivity is reduced.
上記のとおり、先行文献において、ヒドラジド化合物と尿素及び／又は尿素誘導体とを有効成分とするホルムアルデヒド捕捉剤に関する技術は開示されている。しかしながら、ホルムアルデヒド捕捉性能が高いヒドラジド化合物の溶解度を高め、低温析出を防止するという課題を明らかにし、それを解決するための技術は存在しなかった。 As described above, the prior art discloses a technique relating to a formaldehyde scavenger containing hydrazide compounds and urea and / or urea derivatives as active ingredients. However, the problem of increasing the solubility of hydrazide compounds having high formaldehyde scavenging performance and preventing low temperature precipitation has been clarified, and there has been no technique for solving the problem.
本発明は、ヒドラジド化合物と、尿素及び尿素誘導体から構成される群から選択される少なくとも１種とを含み、アルデヒド類を添加したことによって、ヒドラジド化合物の溶解度を向上させたホルムアルデヒド捕捉剤を提供する。捕捉対象物質であるアルデヒド類を添加することによってヒドラジド化合物の溶解度を向上させることができ、その結果、ホルムアルデヒド捕捉効果の高いヒドラジド化合物を高濃度に含んだ捕捉剤を製造することが可能になる。また、アルデヒド類の添加により溶解度が向上することによって、低温環境下において、含まれるヒドラジド化合物が結晶として析出しづらくなる。さらに、吸湿作用を有する物質を添加することによって、従来技術によるホルムアルデヒド捕捉剤と比べてホルムアルデヒド捕捉効果をより高めることができる。 The present invention provides a formaldehyde scavenger containing a hydrazide compound and at least one selected from the group consisting of urea and a urea derivative, and having improved solubility of the hydrazide compound by adding an aldehyde. . The solubility of the hydrazide compound can be improved by adding aldehydes that are substances to be captured, and as a result, a scavenger containing a high concentration of hydrazide compound having a high formaldehyde scavenging effect can be produced. Further, the solubility is improved by the addition of aldehydes, so that the hydrazide compound contained is hardly precipitated as crystals in a low temperature environment. Furthermore, by adding a substance having a hygroscopic action, the formaldehyde scavenging effect can be further enhanced as compared with a formaldehyde scavenger according to the prior art.
また、本発明は、ヒドラジド化合物と、尿素及び尿素誘導体から構成される群から選択される少なくとも１種とを含み、アルデヒド類を添加したことによって、ヒドラジド化合物の溶解度を向上させたホルムアルデヒド捕捉剤の製造方法を提供する。本発明に係るホルムアルデヒド捕捉剤の製造方法は、ヒドラジド化合物を水に溶解し、これにアルデヒド類を添加して前記ヒドラジド化合物と反応させた後、尿素／尿素誘導体を混合することを特徴とする。本方法は、吸湿作用を有する物質をさらに添加することを特徴とする。 The present invention also provides a formaldehyde scavenger comprising a hydrazide compound and at least one selected from the group consisting of urea and a urea derivative, and having improved solubility of the hydrazide compound by adding an aldehyde. A manufacturing method is provided. The method for producing a formaldehyde scavenger according to the present invention is characterized in that a hydrazide compound is dissolved in water, aldehydes are added thereto and reacted with the hydrazide compound, and then urea / urea derivative is mixed. This method is characterized by further adding a substance having a hygroscopic action.
以下に、本発明を詳細に説明する。
本発明のホルムアルデヒド捕捉剤は、建材に使用される接着剤、塗料、防腐剤等に含まれるホルムアルデヒドを捕捉することによって、建材から放出されるホルムアルデヒドの量を低減させるための組成物である。本発明のホルムアルデヒド捕捉剤は、建材に使用される接着剤、塗料、防腐剤等に混合するか、又は、建材に直接含浸、塗布若しくは吹き付けることによって、使用することができる。The present invention is described in detail below.
The formaldehyde scavenger of the present invention is a composition for reducing the amount of formaldehyde released from building materials by capturing formaldehyde contained in adhesives, paints, preservatives and the like used for building materials. The formaldehyde scavenger of the present invention can be used by mixing with adhesives, paints, preservatives and the like used for building materials, or by directly impregnating, coating or spraying the building materials.
本発明のホルムアルデヒド捕捉剤の有効成分として、ヒドラジド化合物を使用する。ヒドラジド化合物は、分子中にヒドラジド基を有する化合物である。ヒドラジド化合物として、分子中に含まれるヒドラジド基の数が１個の化合物であるモノヒドラジド化合物、分子中に含まれるヒドラジド基の数が２個の化合物であるジヒドラジド化合物、分子中に含まれるヒドラジド基の数が３個以上の化合物であるポリヒドラジド化合物が挙げられる。これらのヒドラジド化合物は、単独で又は２種以上を混合して用いることができる。本発明に係るホルムアルデヒド捕捉剤の有効成分として、これらのヒドラジド化合物の中でも、ジヒドラジド化合物が好ましく、２塩基酸ジヒドラジドがさらに好ましく、アジピン酸ジヒドラジドが最も好ましい。 A hydrazide compound is used as an active ingredient of the formaldehyde scavenger of the present invention. A hydrazide compound is a compound having a hydrazide group in the molecule. As a hydrazide compound, a monohydrazide compound in which the number of hydrazide groups contained in the molecule is one, a dihydrazide compound in which the number of hydrazide groups contained in the molecule is 2, and a hydrazide group contained in the molecule The polyhydrazide compound which is a compound whose number is 3 or more is mentioned. These hydrazide compounds can be used alone or in admixture of two or more. Of these hydrazide compounds, the dihydrazide compound is preferred as the active ingredient of the formaldehyde scavenger according to the present invention, dibasic acid dihydrazide is more preferred, and adipic acid dihydrazide is most preferred.
ホルムアルデヒド捕捉剤全体に対するヒドラジド化合物の含有量は、全体を１００重量部とすると、約１重量部〜約５０重量部であることが好ましく、約４重量部〜約１０重量部であることがより好ましい。ヒドラジド化合物の含有量が約１重量部より少ない場合は、ホルムアルデヒド捕捉効果の高いヒドラジド化合物の割合が少なくなるため、十分なホルムアルデヒド捕捉効果が得られない。ヒドラジド化合物の含有量が約５０重量部より多い場合は、常温（２５℃）でもヒドラジド化合物が結晶として析出する。 The content of the hydrazide compound with respect to the whole formaldehyde scavenger is preferably about 1 part by weight to about 50 parts by weight, and more preferably about 4 parts by weight to about 10 parts by weight, when the whole is 100 parts by weight. . When the content of the hydrazide compound is less than about 1 part by weight, the ratio of the hydrazide compound having a high formaldehyde scavenging effect decreases, so that a sufficient formaldehyde scavenging effect cannot be obtained. When the content of the hydrazide compound is more than about 50 parts by weight, the hydrazide compound precipitates as crystals even at room temperature (25 ° C.).
本発明のホルムアルデヒド捕捉剤の有効成分として、尿素及び尿素誘導体から構成される群から選択される少なくとも１種を使用する。本発明に使用される尿素誘導体として、例えば、メチル尿素、エチル尿素、エチレン尿素などが挙げられる。本発明に係るホルムアルデヒド捕捉剤の有効成分として、これらの中でも、尿素及びエチレン尿素を、それぞれ単独で、又は組み合わせて使用することが好ましい。尿素及び尿素誘導体は、単独でアルデヒド捕捉作用を有すると共に、その吸湿性によってヒドラジド類のホルムアルデヒド捕捉効果を向上させる作用がある。したがって、本発明のホルムアルデヒド捕捉剤を吸湿性のないグラスウールなどの繊維系建材に用いた場合でも、十分なホルムアルデヒド捕捉効果が得られる。 As an active ingredient of the formaldehyde scavenger of the present invention, at least one selected from the group consisting of urea and urea derivatives is used. Examples of the urea derivative used in the present invention include methylurea, ethylurea, and ethyleneurea. Among these, urea and ethylene urea are preferably used alone or in combination as the active ingredients of the formaldehyde scavenger according to the present invention. Urea and urea derivatives have an aldehyde scavenging action alone, and also have an action of improving the formaldehyde scavenging effect of hydrazides by their hygroscopicity. Therefore, even when the formaldehyde scavenger of the present invention is used for fiber-based building materials such as glass wool having no hygroscopicity, a sufficient formaldehyde scavenging effect can be obtained.
ホルムアルデヒド捕捉剤全体に対する尿素／尿素誘導体の含有量は、全体を１００重量部とすると、約１重量部〜約５３重量部であることが好ましく、約２重量部〜約８重量部であることがより好ましく、約２重量部〜約６重量部であることがさらに好ましい。尿素及び／又は尿素誘導体の含有量が約１重量部より少ない場合は、尿素／尿素誘導体自体のホルムアルデヒド捕捉効果に対する寄与分が低下することに加えて、ヒドラジド化合物のホルムアルデヒド捕捉効果を向上させる吸湿作用が低下するため、十分なホルムアルデヒド捕捉効果が得られない。尿素及び／又は尿素誘導体の含有量が約５３重量部より多い場合には、常温（２５℃）でも尿素が結晶として析出する。 The content of urea / urea derivative with respect to the total formaldehyde scavenger is preferably from about 1 part by weight to about 53 parts by weight, and preferably from about 2 parts by weight to about 8 parts by weight, based on 100 parts by weight as a whole. More preferably, it is about 2 parts by weight to about 6 parts by weight. When the content of urea and / or urea derivative is less than about 1 part by weight, the moisture absorption action that improves the formaldehyde scavenging effect of the hydrazide compound in addition to the decrease in the contribution of the urea / urea derivative itself to the formaldehyde scavenging effect. As a result, a sufficient formaldehyde scavenging effect cannot be obtained. When the content of urea and / or urea derivative is more than about 53 parts by weight, urea precipitates even at room temperature (25 ° C.).
ヒドラジド化合物と尿素／尿素誘導体との成分比は、尿素を１とすると、約０．１：１〜約１１：１であることが好ましく、約０．５：１〜約５：１であることがより好ましく、約２：１であることが最も好ましい。ヒドラジド化合物と尿素／尿素誘導体との成分比が、約１１：１より大きい場合は、尿素／尿素誘導体の吸湿作用が過小となり、十分なホルムアルデヒド捕捉効果が得られない。ヒドラジド化合物と尿素／尿素誘導体との成分比が、約０．１：１より小さい場合は、尿素／尿素誘導体の吸湿作用が過大となり、ホルムアルデヒド捕捉剤を使用した建材及びその周辺材のかびや結露の問題が生じる可能性がある。 The component ratio of the hydrazide compound to the urea / urea derivative is preferably about 0.1: 1 to about 11: 1, and about 0.5: 1 to about 5: 1, where urea is 1. Is more preferred, and most preferred is about 2: 1. When the component ratio of the hydrazide compound and the urea / urea derivative is greater than about 11: 1, the hygroscopic action of the urea / urea derivative is too small to obtain a sufficient formaldehyde scavenging effect. If the component ratio of the hydrazide compound and the urea / urea derivative is less than about 0.1: 1, the hygroscopic action of the urea / urea derivative will be excessive, and mold and condensation on building materials and their surrounding materials that use formaldehyde scavengers Problems can arise.
以上に示されるような、ヒドラジド化合物と尿素／尿素誘導体とを含むホルムアルデヒド捕捉剤は、既に述べた先行文献にも開示されているように、優れたホルムアルデヒド捕捉性能を有する。しかしながら、こうしたホルムアルデヒド捕捉剤は、ヒドラジド化合物の水に対する溶解度が低いことが原因で、ヒドラジド化合物の含有量増加によるホルムアルデヒド捕捉性能のより一層の向上が難しいという課題が存在する。また、ヒドラジド化合物の低溶解度により、ホルムアルデヒド捕捉剤を含浸、塗布又は吹き付けた建材が、含浸、塗布又は吹き付けの後の製造工程において低温環境に晒されたときに、含まれるヒドラジド化合物が結晶として析出するという課題がある。さらに、上述のような低温貯蔵時におけるホルムアルデヒド捕捉剤の濃度変化の課題や、ホルムアルデヒド捕捉剤を建材に吹き付ける際のノズルの詰まりに関する課題も存在する。これらの課題を解決するために、本発明に係るホルムアルデヒド捕捉剤の成分として、捕捉対象物質であるホルムアルデヒドを含むアルデヒド類を少量添加する。アルデヒド類を添加することによってヒドラジド化合物の溶解度が大きくなり、それにより、ヒドラジド化合物濃度がより高く、かつ、ホルムアルデヒド捕捉効果の高い捕捉剤を製造することが可能になる。また、ヒドラジド化合物の溶解度が大きくなることによって、上述したようなヒドラジド化合物の低温析出の課題などを解決することができる。 The formaldehyde scavenger containing a hydrazide compound and a urea / urea derivative as shown above has excellent formaldehyde scavenging performance as disclosed in the above-mentioned prior literature. However, such a formaldehyde scavenger has a problem that it is difficult to further improve the formaldehyde scavenging performance by increasing the content of the hydrazide compound due to the low solubility of the hydrazide compound in water. In addition, due to the low solubility of the hydrazide compound, when the building material impregnated, coated or sprayed with the formaldehyde scavenger is exposed to a low temperature environment in the manufacturing process after impregnation, coating or spraying, the contained hydrazide compound precipitates as crystals. There is a problem of doing. Furthermore, the subject of the density | concentration change of the formaldehyde scavenger at the time of the above low temperature storage and the subject regarding the clogging of the nozzle at the time of spraying a formaldehyde scavenger on a building material also exist. In order to solve these problems, as a component of the formaldehyde scavenger according to the present invention, a small amount of aldehydes containing formaldehyde as a capture target substance is added. Addition of aldehydes increases the solubility of the hydrazide compound, thereby making it possible to produce a scavenger having a higher hydrazide compound concentration and a high formaldehyde scavenging effect. Moreover, the problem of the low temperature precipitation of the hydrazide compound as described above can be solved by increasing the solubility of the hydrazide compound.
本発明のホルムアルデヒド捕捉剤に添加するアルデヒド類として、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒドなどが挙げられる。これらのアルデヒド類は、単独で又は２種以上を組み合わせて用いることができる。本発明に係るホルムアルデヒド捕捉剤に添加するアルデヒド類として、ホルムアルデヒドが最も好ましい。 Examples of aldehydes added to the formaldehyde scavenger of the present invention include formaldehyde, acetaldehyde, propionaldehyde and the like. These aldehydes can be used alone or in combination of two or more. Formaldehyde is most preferable as the aldehyde added to the formaldehyde scavenger according to the present invention.
ホルムアルデヒド捕捉剤に添加するアルデヒド類の量は、ヒドラジド化合物を１００重量部とすると、約０．１重量部〜３５約重量部であることが好ましく、約０．１重量部〜約１０重量部であることがより好ましく、約２重量部〜約８重量部であることがさらに好ましい。アルデヒド類の添加量が約０．１重量部より少ない場合は、含まれるヒドラジド化合物のヒドラジド基にアルデヒド類が付加する割合が小さくなるため、ヒドラジド化合物の溶解度は十分に大きくならない。アルデヒド類の添加量が約３５重量部より多い場合は、ホルムアルデヒド捕捉に寄与するヒドラジド基の割合が少なくなると共に、ホルムアルデヒド捕捉剤全体に対するヒドラジド化合物の含有量が少ないとき（すなわちアルデヒド添加許容量が大きいとき）であっても、製造時にゲル化（流動性がなくなる現象）が発生し、ホルムアルデヒド捕捉剤として用いることができなくなる。 The amount of aldehydes added to the formaldehyde scavenger is preferably about 0.1 parts by weight to about 35 parts by weight, and about 0.1 parts by weight to about 10 parts by weight, based on 100 parts by weight of the hydrazide compound. More preferred is about 2 parts by weight to about 8 parts by weight. When the amount of aldehyde added is less than about 0.1 part by weight, the ratio of the aldehyde added to the hydrazide group of the hydrazide compound contained becomes small, so the solubility of the hydrazide compound does not increase sufficiently. When the addition amount of aldehydes is more than about 35 parts by weight, the ratio of hydrazide groups contributing to formaldehyde scavenging is reduced, and when the content of hydrazide compounds relative to the whole formaldehyde scavenger is small (that is, the aldehyde addition tolerance is large). However, gelation (a phenomenon in which fluidity is lost) occurs during production, and it cannot be used as a formaldehyde scavenger.
ヒドラジド化合物がホルムアルデヒドを捕捉する際には、水分の介在が必要である。しかしながら、ヒドラジド化合物自体には吸湿性が全くないため、グラスウール又はロックウール等の繊維系建材に使用する場合にヒドラジド化合物をホルムアルデヒド捕捉剤として作用させるためには、吸湿作用を持つ物質を併用する必要がある。本発明のホルムアルデヒド捕捉剤のような、ヒドラジド化合物と尿素／尿素誘導体とを成分とするホルムアルデヒド捕捉剤は、尿素／尿素誘導体が吸湿剤としても作用するため、繊維系建材に使用した場合でも、ヒドラジド化合物が高いホルムアルデヒド捕捉効果を呈する。 When the hydrazide compound captures formaldehyde, it is necessary to intervene with moisture. However, since the hydrazide compound itself has no hygroscopic property, it is necessary to use a substance having a hygroscopic action together with the hydrazide compound in order to act as a formaldehyde scavenger when used for fiber-based building materials such as glass wool or rock wool. There is. The formaldehyde scavenger containing a hydrazide compound and a urea / urea derivative, such as the formaldehyde scavenger of the present invention, acts as a hygroscopic agent because the urea / urea derivative also acts as a hygroscopic agent. The compound exhibits a high formaldehyde scavenging effect.
本発明においては、ホルムアルデヒド捕捉剤の吸湿性をさらに高めるために、吸湿作用を有する物質をホルムアルデヒド捕捉剤に添加することが好ましい。吸湿性をさらに高めることによって、ヒドラジド化合物のホルムアルデヒド捕捉効果をより向上させることができる。本発明に係るホルムアルデヒド捕捉剤に添加する吸湿作用を有する物質は、公知の吸湿性物質又は潮解性物質とすることができ、このような物質として、例えば、塩化カルシウム、塩化マグネシウム、硫酸マグネシウム、亜硫酸水素ナトリウム、水酸化カリウム、リン酸二水素ナトリウム、水酸化ナトリウム、チオ硫酸ナトリウムを挙げることができる。これらの物質のうち、ホルムアルデヒド捕捉剤に添加するものとして、吸湿作用が高くかつ低価格である点で塩化カルシウムが最も好ましい。 In the present invention, in order to further enhance the hygroscopicity of the formaldehyde scavenger, it is preferable to add a substance having a hygroscopic action to the formaldehyde scavenger. By further increasing the hygroscopicity, the formaldehyde scavenging effect of the hydrazide compound can be further improved. The substance having a hygroscopic action to be added to the formaldehyde scavenger according to the present invention can be a known hygroscopic substance or a deliquescent substance. Examples of such substances include calcium chloride, magnesium chloride, magnesium sulfate, and sulfurous acid. Examples thereof include sodium hydrogen, potassium hydroxide, sodium dihydrogen phosphate, sodium hydroxide, and sodium thiosulfate. Of these substances, calcium chloride is most preferable as a substance to be added to the formaldehyde scavenger because of its high hygroscopic action and low price.
ホルムアルデヒド捕捉剤に添加する吸湿性物質の量は、ホルムアルデヒド捕捉剤全体を１００重量部とすると、約２０重量部より少ないことが好ましく、約０．５重量部〜約２重量部であることがさらに好ましく、約１重量部〜約１．５重量部であることが最も好ましい。ホルムアルデヒド捕捉剤に添加する吸湿性物質の量が約２０重量部より多いと、捕捉剤の吸湿性が高くなり過ぎるため、乾燥しづらいという問題がある。 The amount of the hygroscopic substance added to the formaldehyde scavenger is preferably less than about 20 parts by weight, more preferably about 0.5 parts by weight to about 2 parts by weight, with 100 parts by weight of the total formaldehyde scavenger. Preferably, it is about 1 part by weight to about 1.5 parts by weight. When the amount of the hygroscopic substance added to the formaldehyde scavenger is more than about 20 parts by weight, the hygroscopic property of the scavenger becomes too high, and there is a problem that it is difficult to dry.
本発明のホルムアルデヒド捕捉剤には、その効果を損なわない範囲で他の公知のホルムアルデヒド捕捉物質を添加することができる。公知のホルムアルデヒド捕捉物質として、例えば、活性炭、シリカゲル、ゼオライト、パーライトなどを挙げることができる。 Other known formaldehyde scavengers can be added to the formaldehyde scavenger of the present invention as long as the effect is not impaired. Known formaldehyde scavengers include, for example, activated carbon, silica gel, zeolite, pearlite, and the like.
本発明のホルムアルデヒド捕捉剤には、その効果を損なわない範囲で公知の添加剤を添加することができる。公知の添加剤として、例えば、酸化防止剤、殺菌剤、防かび剤、紫外線吸収剤、難燃剤、着色料などを挙げることができる。 A known additive can be added to the formaldehyde scavenger of the present invention as long as the effect is not impaired. Known additives include, for example, antioxidants, bactericides, fungicides, ultraviolet absorbers, flame retardants, colorants and the like.
本発明のホルムアルデヒド捕捉剤は、上記のヒドラジド化合物と、尿素／尿素誘導体と、ホルムアルデヒドとを水に混合することによって、製造することができる。具体的には、まず容器に水を入れ６５℃まで昇温する。次いで、その水に、攪拌しながらヒドラジド化合物を加える。ヒドラジド化合物が完全に溶解した（溶けて透明化した）後、アルデヒド類を添加し、６５℃で３０分間反応させる。この反応によって、ヒドラジド化合物のヒドラジド基の一部にアルデヒド類が付加することになる。このようにして得られた溶液に尿素／尿素誘導体を加えた後、冷却する。その後、必要に応じて、吸湿性物質をさらに添加する。後述の実施例においては、この製造方法で調整したホルムアルデヒド捕捉剤を用いる。 The formaldehyde scavenger of the present invention can be produced by mixing the hydrazide compound, urea / urea derivative, and formaldehyde with water. Specifically, water is first added to the container and the temperature is raised to 65 ° C. The hydrazide compound is then added to the water with stirring. After the hydrazide compound is completely dissolved (dissolved and cleared), aldehydes are added and reacted at 65 ° C. for 30 minutes. By this reaction, aldehydes are added to a part of the hydrazide group of the hydrazide compound. The urea / urea derivative is added to the solution thus obtained and then cooled. Thereafter, a hygroscopic substance is further added as necessary. In the examples described later, a formaldehyde scavenger prepared by this production method is used.
ヒドラジド化合物とアルデヒド類と尿素／尿素誘導体とを混合する順序は、逆にすることもできる。すなわち、尿素／尿素誘導体を水に加え、次いでアルデヒド類を添加し、その後ヒドラジド化合物を加えることによって、本発明のホルムアルデヒド捕捉剤を製造することもできる。また、ヒドラジド化合物と尿素／尿素誘導体とを水に混合し、次いでアルデヒド類を添加することによって、本発明のホルムアルデヒド捕捉剤を製造することもできる。しかしながら、ヒドラジド化合物とアルデヒド類とを先に混合して、アルデヒド類をヒドラジド基のみに反応させることによって、ヒドラジド化合物の溶解度がより高くなる。また、アルデヒド類がヒドラジド基に付加した場合とアミノ基に付加した場合では温度による分解耐性が異なり、アルデヒド類がヒドラジド基に付加した場合の方が再放散のおそれが少ない。したがって、本発明に係るホルムアルデヒド捕捉剤は、水にヒドラジド化合物を加え、アルデヒド類を添加し、最後に尿素／尿素誘導体を加える順序で製造することが好ましい。 The order of mixing the hydrazide compound, the aldehyde and the urea / urea derivative can be reversed. That is, the formaldehyde scavenger of the present invention can also be produced by adding urea / urea derivative to water, then adding aldehydes, and then adding a hydrazide compound. Moreover, the formaldehyde scavenger of this invention can also be manufactured by mixing a hydrazide compound and urea / urea derivative in water, and then adding an aldehyde. However, by mixing the hydrazide compound and the aldehyde first and reacting the aldehyde only with the hydrazide group, the solubility of the hydrazide compound becomes higher. In addition, when the aldehyde is added to the hydrazide group, when it is added to the amino group, the decomposition resistance due to temperature is different, and when the aldehyde is added to the hydrazide group, there is less risk of re-emission. Therefore, the formaldehyde scavenger according to the present invention is preferably produced in the order of adding a hydrazide compound to water, adding an aldehyde, and finally adding a urea / urea derivative.
本発明のホルムアルデヒド捕捉剤を建材に使用するにあたっては、当業者に周知の含浸、塗布、又は吹き付け方法を用いることができる。本発明のホルムアルデヒド捕捉剤をグラスウール、ロックウールなどの繊維系建材に使用する場合は、スプレー装置を用いて本発明のホルムアルデヒド捕捉剤を繊維系建材の表面に吹き付けることによって、含浸又は塗布することができる。 In using the formaldehyde scavenger of the present invention for building materials, impregnation, coating, or spraying methods well known to those skilled in the art can be used. When the formaldehyde scavenger of the present invention is used for fiber-based building materials such as glass wool and rock wool, it may be impregnated or applied by spraying the formaldehyde scavenger of the present invention onto the surface of the fiber-based building material using a spray device. it can.
１．ホルムアルデヒド添加によるホルムアルデヒド捕捉効果と溶解度 1. Formaldehyde scavenging effect and solubility by addition of formaldehyde
（比較例）
全体を１００重量部とし、表１の比較例１、比較例２、比較例３、及び比較例４に示す割合で、表１において「ＡＤＨ」と表記されるアジピン酸ジヒドラジド（日本ファインケム株式会社製）と、表１において「Ｕ」と表記される尿素（三井化学株式会社製）とを水に混合してホルムアルデヒド捕捉剤を調整した。これらのホルムアルデヒド捕捉剤は、捕捉対象物質であるホルムアルデヒドを成分として添加しない比較例（すなわち、公知技術）である。(Comparative example)
Adipic acid dihydrazide (Nippon Finechem Co., Ltd.) expressed as “ADH” in Table 1 at a ratio shown in Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 in Table 1 with 100 parts by weight as a whole. ) And urea represented by “U” in Table 1 (made by Mitsui Chemicals, Inc.) were mixed with water to prepare a formaldehyde scavenger. These formaldehyde scavengers are comparative examples (ie, known techniques) in which formaldehyde, which is a substance to be captured, is not added as a component.
全表面積が約４４０ｃｍ２となるように縦１２．５ｃｍ×横１２．５ｃｍ×高さ２．５ｃｍの大きさに切断した密度６４Ｋのグラスウールの上面に、上述のようにして得られたホルムアルデヒド捕捉剤を約２０ｇ／ｍ２スプレー塗布した後、約２０℃で２４時間自然乾燥させ、試料を準備した。表１において「Ｆ低減率（％）」として表されるホルムアルデヒド捕捉効果は、これらの試料を用いて、ＪＩＳ−Ａ１９０１（建築材料の揮発性有機化合物（ＶＯＣ）、ホルムアルデヒド及び他のカルボニル化合物放散測定法−小形チャンバー法）によってホルムアルデヒド放散速度（表１において「Ｆ放散速度」と表記される）を測定し、ホルムアルデヒド捕捉剤を塗布しない試料（表１において「ブランク」と表記される）のホルムアルデヒド放散速度から、ホルムアルデヒド捕捉剤を塗布した試料のホルムアルデヒド放散速度を引いた値を、ブランクのホルムアルデヒド放散速度で除した値（百分率）によって評価した。ホルムアルデヒド放散速度の測定条件は、測定日数を１日間、チャンバー内の温度を２８℃、相対湿度を５０％、チャンバー容積を２０リットル、換気回数を１時間当たり０．５回とした。サンプリングにはＧＬＰａｋ ｍｉｎｉ ＡＥＲＯＤＮＰＨ（ＧＬサイエンス社製）を用いた。捕集体積は１０Ｌとし、捕集流量は１６７ｍｌ／ｍｉｎとした。Formaldehyde scavenger obtained as described above on the upper surface of a glass wool having a density of 64K cut to a size of 12.5 cm in length, 12.5 cm in width, and 2.5 cm in height so that the total surface area is about 440 cm 2. Was applied by spraying at about 20 g / m 2 , and then naturally dried at about 20 ° C. for 24 hours to prepare a sample. The formaldehyde scavenging effect expressed as “F reduction rate (%)” in Table 1 is measured using these samples, and JIS-A1901 (measurement of volatile organic compounds (VOC) of building materials, formaldehyde and other carbonyl compounds) Formaldehyde emission rate (denoted as “F emission rate” in Table 1) by a small chamber method), and formaldehyde emission of a sample not coated with formaldehyde scavenger (denoted as “blank” in Table 1) The value obtained by subtracting the formaldehyde emission rate of the sample coated with the formaldehyde scavenger from the rate was divided by the blank formaldehyde emission rate (percentage). The measurement conditions of the formaldehyde emission rate were as follows: the measurement days were 1 day, the temperature in the chamber was 28 ° C., the relative humidity was 50%, the chamber volume was 20 liters, and the ventilation frequency was 0.5 times per hour. GLPak mini AERODNPH (GL Science Co., Ltd.) was used for sampling. The collection volume was 10 L, and the collection flow rate was 167 ml / min.
溶解度（水溶解度；ｇ／水１００ｇ）は、飽和溶液１００ｇ中の溶質の質量を測定することによって評価した。具体的には、溶解度は、温度ごとに各々の比較例のホルムアルデヒド捕捉剤の飽和溶液を製造し、その上澄み液の固形分（１０５℃−３Ｈｒｓ乾燥）から算出した。 The solubility (water solubility; g / 100 g of water) was evaluated by measuring the mass of the solute in 100 g of the saturated solution. Specifically, the solubility was calculated from the solid content (105 ° C.—3 Hrs dried) of the supernatant obtained by producing a saturated solution of the formaldehyde scavenger of each comparative example for each temperature.
（実施例）
全体を１００重量部とし、表１の実施例１−１〜４−２に示す割合でアジピン酸ジヒドラジドと尿素とホルムアルデヒドとを水に混合した。これらの成分を混合する方法は、本明細書において上述したとおりである。表１において「Ｆ添加量」と表記されるホルムアルデヒド添加量は、ホルムアルデヒド捕捉剤に含まれるアジピン酸ジヒドラジドを１００重量部としたときの量である。このようにして得られた本発明のホルムアルデヒド捕捉材を比較例と同様の条件でグラスウールにスプレー塗布して試料を準備し、ホルムアルデヒド捕捉効果（「Ｆ低減率」）を評価した。溶解度もまた、比較例と同様の方法で評価した。(Example)
The total was 100 parts by weight, and adipic acid dihydrazide, urea, and formaldehyde were mixed in water in the proportions shown in Examples 1-1 to 4-2 in Table 1. The method of mixing these components is as described above in this specification. The formaldehyde addition amount described as “F addition amount” in Table 1 is an amount based on 100 parts by weight of adipic acid dihydrazide contained in the formaldehyde scavenger. The formaldehyde scavenger of the present invention thus obtained was spray-coated on glass wool under the same conditions as in the comparative example to prepare a sample, and the formaldehyde scavenging effect (“F reduction rate”) was evaluated. The solubility was also evaluated by the same method as in the comparative example.
表１の結果から、アジピン酸ジヒドラジドと尿素とを成分とするホルムアルデヒド捕捉剤に、捕捉対象物質であるホルムアルデヒドを少量添加することによって、低温（５℃）環境下であっても、ホルムアルデヒド捕捉効果を損なうことなくアジピン酸ジヒドラジドの溶解度が大きくなることが判る。また、添加するホルムアルデヒドの量を増加させることによって、ホルムアルデヒド捕捉効果を向上させると同時に、アジピン酸ジヒドラジドの溶解度を増加させることができることも判る。なお、ＡＤＨ：Ｕ＝０．５：１の場合（実施例１−１及び実施例１−２の場合）には、ＡＤＨ１００重量部に対するホルムアルデヒド添加量が約３５重量部より大きくなると製造時にゲル化（流動性が喪失する現象）が発生し、ＡＤＨ：Ｕ＝５：１の場合（実施例４−１及び４−２の場合）には、ＡＤＨ１００重量部に対するホルムアルデヒド添加量が約１０重量部より大きくなると製造時にゲル化する。 From the results in Table 1, by adding a small amount of formaldehyde, which is a target of capture, to formaldehyde scavengers containing adipic acid dihydrazide and urea, the formaldehyde scavenging effect can be obtained even in a low temperature (5 ° C) environment. It can be seen that the solubility of adipic acid dihydrazide is increased without loss. It can also be seen that increasing the amount of formaldehyde added can improve the formaldehyde scavenging effect and at the same time increase the solubility of adipic acid dihydrazide. In addition, in the case of ADH: U = 0.5: 1 (in the case of Example 1-1 and Example 1-2), when the amount of formaldehyde added with respect to 100 parts by weight of ADH becomes larger than about 35 parts by weight, gelation occurs during production. (Phenomenon in which fluidity is lost) occurs, and when ADH: U = 5: 1 (in the case of Examples 4-1 and 4-2), the amount of formaldehyde added to 100 parts by weight of ADH is about 10 parts by weight. When it becomes large, it gels during production.
表２は、表１の実施例１−１〜４−２の各々について、全体を１００重量部としたときに塩化カルシウム（ＣａＣｌ２）を表２に示す割合でさらに添加した場合のＦ低減効果を示す。表２に示される各々の項目についての意義、数値の測定条件、測定方法及び計算方法などは、表１の場合と同様である。表２の結果から、吸湿作用を有する塩化カルシウムを添加することによって、Ｆ低減効果が向上することが判る。なお、実施例７−３について、温度が５℃のときの溶解度を測定すると３１．３ｇ／水１００ｇであった。このことことから、塩化カルシウムの添加によって溶解度が低下しないことが判る。Table 2 shows the F reduction effect when calcium chloride (CaCl 2 ) is further added in the proportion shown in Table 2 when the whole is taken as 100 parts by weight for each of Examples 1-1 to 4-2 in Table 1. Indicates. The significance, numerical measurement conditions, measurement method and calculation method for each item shown in Table 2 are the same as in Table 1. From the results in Table 2, it can be seen that the F reduction effect is improved by adding calcium chloride having a hygroscopic action. In addition, about Example 7-3, when the temperature was 5 ° C., the solubility was 31.3 g / 100 g of water. From this, it can be seen that the addition of calcium chloride does not lower the solubility.
以上のように、本発明に係るホルムアルデヒド捕捉剤は、捕捉対象物質であるホルムアルデヒドを含むアルデヒド類を少量添加することによって、アルデヒド類を添加しない場合と比べて、ヒドラジド化合物の溶解度が増大する。したがって、本発明に係るホルムアルデヒド捕捉剤を使用すると、本発明に係るホルムアルデヒド捕捉剤を含浸、塗布、又は吹き付けた建材の製造工程において建材が低温環境下に晒された場合にも、含まれるヒドラジド化合物が析出しない。また、本発明に係るホルムアルデヒド捕捉剤は、建材に使用される前に低温の貯蔵環境に置かれた場合でもヒドラジド化合物が析出せず、貯蔵中にホルムアルデヒド捕捉剤の濃度が不均一になる問題を解決することができる。さらに、本発明に係るホルムアルデヒド捕捉剤は、吹き付け時のスプレーノズルの目詰まり問題を解決することができる。 As described above, in the formaldehyde scavenger according to the present invention, the solubility of the hydrazide compound is increased by adding a small amount of aldehyde containing formaldehyde which is a target substance to be captured as compared with the case where no aldehyde is added. Accordingly, when the formaldehyde scavenger according to the present invention is used, the hydrazide compound contained even when the building material is exposed to a low temperature environment in the manufacturing process of the building material impregnated, coated, or sprayed with the formaldehyde scavenger according to the present invention. Does not precipitate. Further, the formaldehyde scavenger according to the present invention has a problem that the hydrazide compound does not precipitate even when placed in a low temperature storage environment before being used for building materials, and the concentration of the formaldehyde scavenger becomes non-uniform during storage. Can be solved. Furthermore, the formaldehyde scavenger according to the present invention can solve the problem of clogging of the spray nozzle during spraying.
さらに、本発明に係るホルムアルデヒド捕捉剤は、含まれるヒドラジド化合物の溶解度を増大させることができるため、ヒドラジド化合物の高濃度化が可能となる。ヒドラジド化合物の高濃度化が可能になれば、高濃度の状態で捕捉剤を搬送し、最終製品を製造する際に希釈することができるため、輸送コストを低減することが可能になる。また、本発明に係るホルムアルデヒド捕捉剤は、高濃度化が可能になれば、建材に付着する有効成分量すなわちヒドラジド化合物の量を減少させることなくホルムアルデヒド捕捉剤の建材への吹き付け量を減らすことができるため、吹き付け後の乾燥温度を低下させることが可能になり、使用エネルギー削減に寄与する。 Furthermore, since the formaldehyde scavenger according to the present invention can increase the solubility of the contained hydrazide compound, it is possible to increase the concentration of the hydrazide compound. If the concentration of the hydrazide compound can be increased, the capture agent can be transported in a high concentration state and diluted when the final product is manufactured, so that the transportation cost can be reduced. In addition, the formaldehyde scavenger according to the present invention can reduce the amount of sprayed formaldehyde scavenger onto the building material without reducing the amount of active ingredient adhering to the building material, that is, the amount of hydrazide compound, if the concentration can be increased. Therefore, it becomes possible to reduce the drying temperature after spraying, which contributes to reduction of energy consumption.
Claims (9)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007035378 | 2007-02-15 | ||
| JP2007035378 | 2007-02-15 | ||
| PCT/JP2008/000214 WO2008099604A1 (en) | 2007-02-15 | 2008-02-13 | Formaldehyde scavenger and method for production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP4256467B2 true JP4256467B2 (en) | 2009-04-22 |
| JPWO2008099604A1 JPWO2008099604A1 (en) | 2010-05-27 |
Family
ID=39689851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008533800A Active JP4256467B2 (en) | 2007-02-15 | 2008-02-13 | Formaldehyde scavenger and method for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4256467B2 (en) |
| WO (1) | WO2008099604A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480116A (en) * | 2012-07-12 | 2014-01-01 | 唐赫 | Formaldehyde scavenger and preparation method thereof |
| EP3050618A4 (en) * | 2013-09-27 | 2017-06-14 | Toyobo Co., Ltd. | Aldehyde removal material |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2946265B1 (en) * | 2009-06-03 | 2012-12-21 | Saint Gobain Technical Fabrcis Europ | MATERIAL OF MINERAL FIBERS COMPRISING A FORMALDEHYDE-FRIENDLY AGENT AND METHODS OF MAKING |
| US8500880B2 (en) * | 2009-11-24 | 2013-08-06 | Corning Incorporated | Amino acid salt articles and methods of making and using them |
| US8163069B2 (en) | 2009-11-24 | 2012-04-24 | Corning Incorporated | Carboxylic acid salt articles and methods of making and using them |
| JP2014503340A (en) * | 2010-11-15 | 2014-02-13 | コーニング インコーポレイテッド | Carboxylate articles and methods of making and using the same |
| CN104383657A (en) * | 2014-11-25 | 2015-03-04 | 成都顺发消洗科技有限公司 | Preparation method of formaldehyde scavenging agent for urea-formaldehyde adhesive artificial board |
| CN104623855B (en) * | 2015-02-06 | 2018-02-06 | 山东恒诺环保科技有限公司 | A kind of plant type formaldehyde scavenger and preparation method |
| CN104841257B (en) * | 2015-04-14 | 2017-04-19 | 张家港大塚化学有限公司 | Safe formaldehyde removing solution, and preparation method thereof |
| CN106366974A (en) * | 2016-10-26 | 2017-02-01 | 东北林业大学 | Multifunctional preparation for controlling formaldehyde emission |
| CN108748530B (en) * | 2018-05-18 | 2020-01-17 | 河北霍夫曼新材料科技有限公司 | Preparation method of wood mildew preventive |
| CN110302645A (en) * | 2019-08-10 | 2019-10-08 | 深圳市至霸化工有限公司 | A kind of preparation method of formaldehyde scavenger |
| CN113088216A (en) * | 2021-05-06 | 2021-07-09 | 中山市森林家新材料科技有限公司 | Formaldehyde removal additive composition and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56105905A (en) * | 1980-01-29 | 1981-08-22 | Otsuka Kagaku Yakuhin | Formalin adsorbent |
| JP2001164235A (en) * | 1999-09-30 | 2001-06-19 | Kyokutoo International:Kk | Scavenger for formaldehyde, method for treating wooden plate and wooden plate |
| JP2002273145A (en) * | 2001-03-15 | 2002-09-24 | Mariko Koizumi | Formaldehyde scavenger, method for treating woody plate, and woody plate |
| JP2004189824A (en) * | 2002-12-10 | 2004-07-08 | Nippon Kasei Chem Co Ltd | Formaldehyde scavenger |
| JP2004189873A (en) * | 2002-12-11 | 2004-07-08 | Nippon Kasei Chem Co Ltd | Formaldehyde scavenger composition |
| JP4407190B2 (en) * | 2003-07-28 | 2010-02-03 | パナソニック電工株式会社 | Aldehyde catcher agent |
| JP2006028366A (en) * | 2004-07-16 | 2006-02-02 | Nippon Kasei Chem Co Ltd | Formaldehyde scavenger and woody material |
| EA013599B1 (en) * | 2005-07-06 | 2010-06-30 | Иппоса Ойл Индастриз Ко., Лтд. | Aldehyde (aldehydes) capture material and process for production of plywood with the same |
-
2008
- 2008-02-13 WO PCT/JP2008/000214 patent/WO2008099604A1/en active Application Filing
- 2008-02-13 JP JP2008533800A patent/JP4256467B2/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480116A (en) * | 2012-07-12 | 2014-01-01 | 唐赫 | Formaldehyde scavenger and preparation method thereof |
| EP3050618A4 (en) * | 2013-09-27 | 2017-06-14 | Toyobo Co., Ltd. | Aldehyde removal material |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008099604A1 (en) | 2008-08-21 |
| JPWO2008099604A1 (en) | 2010-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4256467B2 (en) | Formaldehyde scavenger and method for producing the same | |
| EP2081676B1 (en) | Method of forming an acid-impregnated activated carbon and its use | |
| JP4071825B2 (en) | Compositions and methods for protecting wood products | |
| US11000824B2 (en) | Treated activated carbon for removal of airborne organic and inorganic contaminants | |
| ES2529356T3 (en) | Procedure to reduce the emission of volatile organic compounds from wood derivatives and wood derivatives | |
| JP6851834B2 (en) | Aldehyde adsorbent | |
| JP2001000524A (en) | Adsorbent of lower aldehydes | |
| JP2009056449A (en) | Lower aldehyde adsorbent | |
| CN104174267A (en) | Aromatic air purification powder and preparation method thereof | |
| WO2007083578A1 (en) | Formaldehyde scavenger, deodorant composition, deodorant solution and wooden material | |
| KR102397381B1 (en) | Composition with air purification function | |
| JP2004105854A (en) | Adsorbing material and method for production thereof | |
| CN109304081A (en) | A kind of environment friendly artificial board material formaldehyde eliminating agent | |
| JP2010137113A (en) | Adsorbent for lower aldehyde, and method of producing the same | |
| JP2006028366A (en) | Formaldehyde scavenger and woody material | |
| JP5341871B2 (en) | Aldehyde adsorbent and method for producing the same | |
| KR101970755B1 (en) | Coating composition of PVC wallpaper having sick house low reduction effect and PVC wallpaper using the same | |
| JP2005097340A (en) | Aldehyde catcher | |
| CN109092024A (en) | A kind of oil-soluble formaldehyde scavenger | |
| KR20100096376A (en) | Preparation method of deodorant for removing polymer-derived odor and deodorant obtained thereby | |
| KR102428140B1 (en) | Deodorizing filter coating composition for air cleaners and deodorizing filter using the same | |
| JP2008136601A (en) | Deodorant composition, deodorant solution and wooden material | |
| JP2003169841A (en) | Deodorant and method of preparing the same | |
| WO2015072263A1 (en) | Adsorbent | |
| JP2004189824A (en) | Formaldehyde scavenger |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090113 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090129 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120206 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4256467 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120206 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130206 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140206 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |