JP4403111B2 - Formaldehyde scavenger and building material using the same - Google Patents

Description

  The present invention relates to a formaldehyde scavenger, and more particularly to a formaldehyde scavenger having an excellent formaldehyde scavenging effect over a long period of time and a building material using the same.

  In recent years, high heat insulation and high airtightness of residential buildings have been recommended from the viewpoint of energy saving. On the other hand, the living environment is being damaged by volatile organic compounds (VOC) released from organic materials used for building materials.

  In particular, aldehyde-condensable thermosetting resins used in building materials such as structural plywood, furniture, building material paints, adhesives, and inorganic fiber heat-absorbing sound-absorbing materials are the cause of “sick house syndrome” that is becoming a social problem. In some cases, a large amount of formaldehyde was released.

  Therefore, in order to maintain a comfortable residential environment, it is particularly required to suppress the emission of formaldehyde. For example, an attempt has been made to change the design of organic materials used for building materials to organic materials that do not readily diffuse formaldehyde. Has been made. However, it is difficult to find an organic material that can replace aldehyde-condensable thermosetting resin due to problems such as difficulty in achieving the same performance as aldehyde-condensable thermosetting resin, increased material costs, or changes in processing equipment. Met.

  Attempts have also been made to suppress the emission of formaldehyde released from building materials, and various proposals have been made on formaldehyde scavengers used to trap formaldehyde released from building materials.

  As formaldehyde scavengers, hydrazide compounds, azole compounds, azine compounds, etc. have been widely used in the past, but these compounds are relatively expensive, and if these compounds are used, the cost is low. However, the economy is likely to be impaired.

Therefore, in order to reduce costs and improve the effect of capturing formaldehyde, for example, in Patent Document 1 below, at least one selected from hydrazide compounds, azole compounds, and azine compounds, and urea and its derivatives It is disclosed to use at least one selected in combination.
JP 2002-35098 A

  However, many of the hydrazide compounds, azole compounds, azine compounds, urea and their derivatives are solid compounds at room temperature, and construction such as plywood using aldehyde condensable resin, heat insulating sound absorbing material for inorganic fibers, etc. In order to use it as a formaldehyde scavenger in a material, it was necessary to use it by dissolving it in a solvent such as water.

  For example, when water is used as a medium, a drying process is required after applying a formaldehyde scavenger to a building material, so that the production process becomes complicated and productivity tends to be impaired. Furthermore, since melamine-urea resin, phenol-urea resin, and the like promote water hydrolysis and release formaldehyde, in building materials using these binders, VOC emissions such as formaldehyde are released. Sometimes increased over time.

  In addition, since solid formaldehyde scavengers are gaseous formaldehyde, in order to efficiently promote the gas-solid reaction between formaldehyde and formaldehyde scavengers and to obtain the desired formaldehyde scavenging effect, the amount of adhesion to building materials must be reduced. There is a need to do more. However, since it is solid, the formaldehyde scavenger tends to fall off from the applied building material, and it has been necessary to apply an excessive amount of formaldehyde scavenger in advance, so there is a problem that the economy tends to be impaired. It was.

  Accordingly, an object of the present invention is to provide a formaldehyde scavenger capable of maintaining a superior formaldehyde scavenging effect over a long period of time and simplifying the drying process when applied to a building material, and a building material using the same. There is.

In achieving the above object, the formaldehyde scavenger of the present invention comprises a polyamidoamine having a total amine number of 100 mgKOH / g or more and a solubility in water of less than 20 g / liter at 25 ° C. and a liquid at 25 ° C. It is a composition obtained by mixing with a polyol having two or more hydroxyl groups.

  According to this, since the polyamidoamine has many amino groups, imino groups, or amide groups, it has a high formaldehyde scavenging effect and has low water solubility and hydrophobicity. Thus, it is possible to suppress re-release of formaldehyde once trapped, and to maintain an excellent formaldehyde trapping effect over a long period of time.

  In addition, since the polyol used in combination with the polyamidoamine has a lower surface tension than water, it has excellent fluidity and can cover a large area even with a relatively small coating amount. Therefore, formaldehyde can be efficiently captured. Furthermore, depending on the reaction conditions, the polyol reacts with formaldehyde to produce acetals, so that the formaldehyde capturing effect is improved.

  The composition obtained by mixing the polyamidoamine and the polyol has a viscosity excellent in coating workability without using water, so that the drying process can be simplified or omitted. is there.

  Therefore, the formaldehyde scavenger of the present invention has a high formaldehyde scavenging effect over a long period of time even with a very small amount of application, and the amount of formaldehyde scavenger used can be reduced. Further, since the coating workability is excellent without using water, the drying process can be simplified or omitted.

  The polyamidoamine is preferably a condensate of an alkylene polyamine having two or more amino groups in the molecule and an aliphatic dicarboxylic acid having 6 or more carbon atoms. According to this, since polyamidoamine is favorable in viscosity, it is easy to apply to building materials and the like. Furthermore, since the hydrophobicity is also high, after formaldehyde is captured by a chemical reaction, it is possible to suppress re-release of formaldehyde captured by moisture in the air, and an excellent formaldehyde capturing effect can be maintained over a long period of time.

  The polyol is preferably an alkylene diol or a polyoxyalkylene diol. According to this, the fluidity | liquidity of a polyamidoamine can be improved, without impairing the trapping effect of formaldehyde, and the application workability | operativity to building materials etc. can be improved.

  Moreover, it is preferable that the said composition is a composition obtained by mixing the said polyamidoamine and the said polyol so that polyamidoamine / polyol may be set to 5 / 95-30 / 70 by mass ratio. According to this, the viscosity of the formaldehyde scavenger of the present invention does not become too high, and it is easy to adjust to a viscosity that is easy to apply. For example, the formaldehyde scavenger is applied to building materials such as plywood and inorganic fiber heat-absorbing sound absorbing material. At that time, it can be applied by flowing so as to cover a large area in a short time.

On the other hand, the building material subjected to the formaldehyde emission suppression treatment of the present invention is a building material obtained by molding and curing by attaching a binder whose main component is an aldehyde condensable thermosetting resin. The formaldehyde scavenger described in one is attached in an amount of 1 to 20 g / m ^{2 in} solid content with respect to the surface area of the building material. Moreover, it is preferable that the said building material is an inorganic fiber heat insulation sound-absorbing material or a plywood. According to this, the release of formaldehyde from building materials can be suppressed, and the effect can be demonstrated over a long period of time, so that a comfortable living environment can be provided, and the conventional formaldehyde capture Since it is cheaper than the agent, the material cost can be kept low.

  The formaldehyde scavenger of the present invention has a high formaldehyde scavenging effect even in a small amount of application, and can maintain the effect over a long period of time.

  In addition, building materials such as plywood and inorganic fiber heat-absorbing sound-absorbing materials with formaldehyde scavengers have standards that formaldehyde emission speed does not apply to the use restrictions of the Building Standards Act, such as housing walls, ceilings, etc. It can be used for heat insulating materials, floating floor heat insulating materials and the like without any hindrance and can provide a comfortable living environment.

  The formaldehyde scavenger of the present invention is a composition obtained by mixing polyamidoamine and polyol.

  Although this composition is a liquid composition at 25 ° C., there is a possibility that a part of the polyamidoamine and the polyol are reacted because heat is generated when the polyamidoamine and the polyol are mixed. Therefore, although the details are not clear, the composition may contain a reaction product of polyamidoamine and polyol in addition to polyamidoamine and polyol.

  The polyamidoamine in the formaldehyde scavenger of the present invention is required to have a total amine value of 100 mgKOH / g or more, preferably 120 to 250 mgKOH / g, more preferably 150 to 250 mgKOH / g.

  If the amine value of polyamidoamine is 100 mgKOH / g or more, the formaldehyde scavenging effect is high, and the effect proposed by the present invention can be obtained. On the other hand, if the total amine value is less than 100 mgKOH / g, the formaldehyde scavenging effect per unit weight becomes insufficient, and in order to obtain the desired formaldehyde scavenging effect, a large amount of formaldehyde scavenger is a target building material, etc. In addition to being uneconomical, there are cases in which adverse effects such as contamination due to formaldehyde scavengers may occur. Here, the total amine value is the amount of potassium hydroxide equivalent to perchloric acid necessary to neutralize all basic nitrogen of amino group, imino group and amide group contained in the molecule per unit mass. It is defined by mass.

  The solubility of polyamidoamine in water needs to be less than 50 g / liter at 25 ° C., preferably less than 20 g / liter, and more preferably less than 5 g / liter.

  When a highly hydrophilic compound is used as the formaldehyde scavenger, moisture in the air is attracted and absorbed. The absorbed moisture may have various effects on the cured aldehyde condensable thermosetting resin or formaldehyde scavenger.

  For example, adhesives, paints, or binders based on aldehyde-condensable thermosetting resins use acid catalysts to reduce curing time and improve productivity. It exhibits acidity, and it becomes easy to proceed with curing of the aldehyde condensable thermosetting resin again. If all the methylol groups in the aldehyde-condensable thermosetting resin are complete, no new formaldehyde will be generated or released, but if the condensation reaction between methylol groups is incomplete, a new reaction will occur. Progresses, generating and releasing formaldehyde.

  In addition, when the urea resin is contained in the aldehyde condensable thermosetting resin component, the urea resin component is sequentially hydrolyzed by the moisture absorbed, and aldehydes such as formaldehyde as well as ammonia and amines are also present. It may be generated / released.

  Furthermore, since the reaction of amino group, imino group, and amide group with formaldehyde is not necessarily a strong reaction, a reversible reaction occurs due to moisture, and formaldehyde is re-released little by little over time. Sometimes.

  Therefore, it has been found that it is preferable to use a hydrophobic material as the formaldehyde scavenger in maintaining the formaldehyde scavenging effect over a long period of time.

  If the solubility of polyamidoamine in water is less than 50 g / liter at 25 ° C., it is difficult to absorb moisture in the air. If the polyamidoamine has a solubility in water within the above range, the captured formaldehyde is re-released. It is difficult to cause formaldehyde to be captured over a long period of time.

  The polyamidoamine in the present invention is not particularly limited as long as it has the above-mentioned configuration, but is a condensate of an alkylene polyamine having 2 or more amino groups in the molecule and an aliphatic dicarboxylic acid having 6 or more carbon atoms. (Hereinafter simply referred to as “condensate”). Further, the molecular weight of the condensate is not particularly limited as long as the total amine value and the solubility in water are within the above-mentioned ranges, but from the viewpoint of the viscosity and fluidity of the condensate, it should be a liquid substance. Is preferred.

  This condensate has the above-mentioned performance, but is a low-viscosity polyamidoamine, so when applied to building materials, etc., it has high fluidity and wettability and can cover a large surface area even with a small amount. it can.

  The alkylene polyamine used for the condensate preferably has 2 or more amino groups in the molecule, and more preferably has 2 to 6 amino groups.

Examples of such alkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, methylaminopropylamine, 1,2-propylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1, Examples include 2,3-triaminopropane and 1,2,4-triaminobutane. Among them, the alkylene polyamine represented by the chemical formula of NH ₂ — (CH ₂ —CH ₂ —NH) _n —CH ₂ —CH ₂ —NH ₂ increases the number of basic nitrogens per unit mass, and the trapping effect of formaldehyde Is more preferable.

  In addition, when the aliphatic dicarboxylic acid used in the condensate has 6 or more carbon atoms, the aliphatic dicarboxylic acid has high hydrophobicity and water solubility is reduced. As a result, the water solubility is low. A polyamidoamine is obtained. The aliphatic dicarboxylic acid preferably has 6 to 60 carbon atoms.

  Examples of such aliphatic dicarboxylic acids include dimer acids synthesized from adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and unsaturated fatty acids. Among them, dimer acid having high hydrophobicity is used. More preferred. Dimer acid is synthesized from unsaturated fatty acid having 18 carbon atoms as a main raw material, and therefore contains a small amount of trimer acid (carbon number 54) and monomer acid (carbon number 18). The dimer acid in the invention refers to those containing these.

  In the present invention, in addition to the aliphatic dicarboxylic acid, aromatic carboxylic acids such as trimellitic acid and pyromellitic acid may be used in combination with the aliphatic dicarboxylic acid. The amount of aromatic carboxylic acid used is preferably 30 parts by mass or less with respect to 100 parts by mass of the aliphatic dicarboxylic acid.

  The polyol in the formaldehyde scavenger of the present invention is a polyol that is liquid at 25 ° C. and has two or more hydroxyl groups. This polyol is a solvent for dissolving the polyamidoamine and improving the fluidity at the time of coating, and has a formaldehyde scavenging effect that reacts with formaldehyde to form acetal although it is not immediately effective. It is. In the present invention, a polyol having a liquid property at 25 ° C. refers to a polyol having a melting point or freezing point of 25 ° C. or less.

  Such a polyol is preferably an alkylene diol or a polyoxyalkylene diol, and specifically includes ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and the like. It is done. Triols such as glycerin can also be used as polyols other than the above, but since glycerin uses aldehydes in its production process, aldehyde may remain in glycerin, and formaldehyde scavenging effect. It is preferable to avoid the use of glycerin because it may be damaged.

  And as a polyol in this invention, diethylene glycol is especially preferable.

  The formaldehyde scavenger of the present invention is preferably a composition obtained by mixing the polyamidoamine and the polyol so that the polyamidoamine / polyol is 5/95 to 30/70 by mass ratio. More preferably, it is a composition obtained by mixing so as to be 10/90 to 20/80.

  When the mixing amount of the polyamidoamine is less than 5 by mass ratio, in order to obtain a desired formaldehyde scavenging effect, the coating amount increases, and further, a drying step after coating may be required. This is a problem in terms of productivity. Further, when the mixing amount of the polyamidoamine exceeds 30, the viscosity of the formaldehyde scavenger tends to increase, and when applied, the fluidity is impaired, the application efficiency is inferior, and the area to be coated In some cases, the desired formaldehyde scavenging effect cannot be obtained, and the tackiness due to the increase in viscosity is increased, resulting in contamination.

  Moreover, in the formaldehyde scavenger of this invention, you may add water, an epoxy resin, an inorganic filler, etc. as needed.

  The formaldehyde scavenger of the present invention has sufficient fluidity even without the addition of water and is excellent in application workability, but immediately after the curing oven step of the aldehyde condensable thermosetting resin applied to building materials and the like In addition, water may be added for the purpose of reducing the danger of ignition when applying the scavenger or improving the working environment by reducing the odor of the polyamidoamine.

  And it is preferable that the addition amount of water is less than 20 mass parts with respect to 100 mass parts of formaldehyde scavengers. If the amount of water added exceeds 20 parts by mass, the miscibility between the polyamidoamine and the polyol is impaired, the polyamidoamine is separated, and the scavenger becomes cloudy, making it difficult to apply. The remaining amount is increased, and for the reasons mentioned above, a reduction of the formaldehyde scavenging effect or a drying step is required.

  In addition, when it is desired to increase the viscosity after application of the formaldehyde scavenger of the present invention and suppress fluidity over time, it is preferable to add an epoxy resin that is a liquid at room temperature.

  Originally, polyamidoamine is used as a curing agent for epoxy resin, and therefore, it easily reacts with epoxy resin even at room temperature. Therefore, when the epoxy resin is mixed with the formaldehyde scavenger in advance, the epoxy resin cross-linking reaction proceeds to increase the viscosity of the scavenger, making it difficult to apply. Therefore, the epoxy resin is added to the formaldehyde scavenger of the present invention. When adding, it is preferable to add just before apply | coating to a building material etc. By doing so, it is possible to increase the viscosity after application and flow without impairing the application workability of the formaldehyde scavenger.

  The addition amount of the epoxy resin is such that when the amino group, imino group, amide group, etc. in the polyamidoamine are consumed excessively by the epoxy group of the epoxy resin, the scavenging effect of formaldehyde is lowered. It is preferable to adjust the addition amount so that about% is consumed by the epoxy group of the epoxy resin.

  In addition, when the formaldehyde scavenger of the present invention is applied by a spray method and then does not want to flow, it is preferable to add an inorganic filler in advance.

  By adding an inorganic filler, the viscosity of the formaldehyde scavenger apparently increases, but when applied with a strong external force such as spraying, the viscosity decreases, so that the coating workability does not decrease.

  Such inorganic filler is not particularly limited, but preferably swelled by water such as smectite such as montmorillonite, beidellite, nontrolite, hectorite, saponite, vermiculite, halosite, apatalite, sepiolite, etc. Furthermore, an organophilic montmorillonite treated with an alkyl ammonium salt is more preferable.

  And the addition amount of the said inorganic filler does not have limitation in particular, It can adjust suitably according to the installation of the application | coating process.

The total content of water, epoxy resin, and inorganic filler in the formaldehyde scavenger can be arbitrarily adjusted according to the workability in the coating process.

  Next, the building material provided with the formaldehyde scavenger will be described.

  The building material subjected to the formaldehyde emission suppression treatment of the present invention is the above-mentioned formaldehyde scavenger attached to a building material obtained by molding and curing a binder whose main component is an aldehyde condensable thermosetting resin. It is obtained.

  Examples of the building material include an inorganic fiber heat-absorbing and sound-absorbing material, plywood, particle board, MDF, wallpaper, paint, and various finishing materials. These building materials generally use an aldehyde condensable thermosetting resin from the viewpoint of product physical properties and economy. For example, in an inorganic fiber heat-absorbing sound-absorbing material, as a component of a binder and in a plywood. Is used as an adhesive component.

Then, as the aldehyde condensable thermosetting resin used in such building materials, resol type phenolic resins, resol type phenol - urea resins, melamine - urea resins and the like, both formaldehyde generated in the curing process To do.

  Therefore, since formaldehyde is gradually diffused with time in such a building material, the formaldehyde scavenger is applied to the building material in order to suppress their release.

The amount of formaldehyde scavenger attached must be 1 to ²⁰ g / m ^{2 in} solid content with respect to the surface area of the building material. For example, the building material has a low bulk density such as an inorganic fiber heat-absorbing sound absorbing material. In the case of a material, it is preferable to adhere 1 to 10 g / m ² . For example, in the case of woody building materials such as plywood, 5 to 20 g / m ² is preferably attached.

When the adhesion amount of the formaldehyde scavenger is less than 1 g / m ^{2 with} respect to the surface area of the building material, for example, in a high-density product having a relatively high density and a large amount of binder adhesion, such as a glass wool product, It is difficult to reduce to a formaldehyde emission rate of the F ☆☆☆☆ grade, and although it is small, it may have an unfavorable effect on the living environment. Further, even if the adhesion amount exceeds 20 g / m ² with respect to the surface area of the building material, the application amount of the formaldehyde scavenger is only excessive, so that the improvement in the effect is not recognized so much that the productivity is inferior. Therefore, the adhesion amount of the formaldehyde scavenger of the present invention is set to 1 to ²⁰ g / m ² in terms of solid content with respect to the surface area with respect to the total amount of the target building material.

  Examples of the formaldehyde scavenger coating method include a roll coater method, a curtain flow coater method, and a spin coater method. However, for substrates having relatively large dimensions such as plywood, air The spray method is preferable, and it is also preferable to apply a spin coater method to a relatively small substrate such as that used for furniture members, in addition to the spray method. Further, when there is sufficient drying equipment, an impregnation method can also be used.

As described above, the building material of the present invention has a small amount of formaldehyde released despite being cured and molded by attaching a binder which is an aldehyde-condensable thermosetting resin, and the chamber of JIS-A1901. In a test based on the law, the formaldehyde emission rate can be 5 μg / m ² h or less.

Here, the classification according to the formaldehyde emission rate stipulated in the above JIS is divided into three stages from F ☆☆ to F ☆☆☆☆. When the formaldehyde emission rate is 5 μg / m ² h or less, F ☆☆☆ ☆ ^{type, 5μg / m 2 h~20μg / m} 2 h or less when F ☆☆☆ types are classified into a case F ☆☆ type below ^{20μg / m 2 h~120μg / m 2} h. Therefore, the building material of the present invention can sufficiently satisfy the F ☆☆☆☆ grade, which is a level that does not cause a problem with respect to the living environment, as stipulated in the Building Standard Law.

  Next, the application process of the formaldehyde scavenger will be described taking an inorganic fiber heat-insulating material as an example.

  First, the molten inorganic raw material is fiberized with a fiberizing apparatus, and immediately after that, the above-mentioned aqueous binder for inorganic fibers is applied to the inorganic fibers. Next, the inorganic fiber to which the aqueous binder for inorganic fibers is applied is deposited on a perforated conveyor to form a bulky inorganic fiber heat insulating material intermediate, and the upper and lower sides are spaced so as to have a desired thickness. It feeds into a pair of perforated conveyors or the like and heats it while narrowing it, and cures the aqueous binder for inorganic fibers to form an inorganic fiber heat insulating sound absorbing material. Next, a skin material or the like is coated as necessary, and the inorganic fiber heat insulating sound absorbing material is cut into a desired width and length to obtain a product. Hereinafter, each step will be described.

First, the inorganic fiber used in the present invention is not particularly limited, and glass wool, rock wool, and the like that are used in ordinary heat-absorbing sound-absorbing materials can be used. Various methods such as a flame method, a blow-off method, and a centrifugal method (also referred to as a rotary method) can be used as a method for forming inorganic fibers. In particular, when the inorganic fiber is glass wool, the centrifugal method is preferably used. In addition, the density of the target inorganic fiber heat-insulating material may be a density used in ordinary heat-insulating materials and sound-absorbing materials, and is preferably in the range of 5 to 300 kg / m ³ .

  Next, in order to impart a binder to the inorganic fiber, it can be applied and sprayed using a spray device or the like. The amount of the binder applied varies depending on the density and use of the inorganic fiber heat-absorbing sound absorbing material, but the solid content is preferably in the range of 0.5 to 15% by mass based on the mass of the inorganic fiber heat-absorbing sound absorbing material to which the binder is applied. The range of 5-9 mass% is more preferable.

  The timing of applying the aqueous binder to the inorganic fiber sound-absorbing heat insulating material may be any time as long as it is after fiberization, but it is preferable to apply it immediately after fiberization for efficient application.

  The inorganic fiber to which the binder is applied by the above process is deposited on the perforated conveyor to form a bulky inorganic fiber intermediate. Here, when depositing on the perforated conveyor, it is more preferable to suck with a suction device from the opposite side of the perforated conveyor on which the inorganic fibers are deposited. After that, the inorganic fiber intermediate that continuously moves on the perforated conveyor is sent to a pair of upper and lower perforated conveyors and the like that are spaced so as to have a desired thickness, and at the same time, heated hot air is used as a binder. The thermosetting resin precursor contained is cured to form an inorganic fiber heat-absorbing sound-absorbing material into a mat shape, and then cut into desired widths and lengths.

  Although the temperature which hardens the aldehyde condensable thermosetting resin contained in a binder is not specifically limited, 200-350 degreeC may be sufficient. Moreover, heating time is suitably performed in 30 second-10 minutes according to the density and thickness of an inorganic fiber heat-insulating sound-absorbing material.

  The formaldehyde scavenger of the present invention is preferably applied to the inorganic fiber heat-absorbing sound-absorbing material immediately after this curing process.

  Application is sprayed using atomized air. Although the hydraulic spray may be used, the former air spray method is preferable when finely adjusting the coating amount or relatively widening the spray range.

  And this inorganic fiber heat-insulation sound-absorbing material may be used with the form as it is, and may be coat | covered and used for a skin material. As the skin material, paper, synthetic resin film, metal foil film, non-woven fabric, woven fabric, or a combination thereof can be used.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Preparation of formaldehyde scavenger]
Example 1
15 parts by mass of polyamidoamine obtained by condensing pentaethylenehexamine and dimer acid (total amine value 200 mgKOH / g, solubility in water 5 g / liter) and 85 parts by mass of diethylene glycol were mixed and stirred. The formaldehyde scavenger of Example 1 was obtained.

(Example 2)
20 parts by mass of polyamidoamine obtained by condensing triethylenetetramine with adipic acid and trimellitic acid (total amine number 120 mgKOH / g, solubility in water 1 g / liter), 70 parts by mass of ethylene glycol, After mixing and stirring, 10 parts by mass of water was added to obtain the formaldehyde scavenger of Example 2.

( Reference Example 1 )
20 parts by mass of polyamidoamine obtained by condensing dipropylenetriamine and diethylenetriamine with azelaic acid (total amine value 250 mgKOH / g, solubility in water 40 g / liter) and 80 parts by mass of diethylene glycol were mixed. Thereafter, 5 parts by mass of bisphenol A diglycidyl ether (epoxy equivalent: 340 g / eq) was added to obtain the formaldehyde scavenger of Reference Example 1 .

(Comparative Example 1)
15 parts by mass of polyamidoamine obtained by condensing diethylenetriamine and adipic acid (total amine value 260 mgKOH / g, solubility in water 125 g / liter) and 75 parts by mass of diethylene glycol were mixed and stirred, 10 parts by mass was added to obtain a formaldehyde scavenger of Comparative Example 1.

(Comparative Example 2)
15 parts by mass of adipic acid dihydrazide was mixed and dissolved in 85 parts by mass of water to obtain a formaldehyde scavenger of Comparative Example 2.

(Comparative Example 3)
15 parts by mass of ethylene urea was dissolved in 85 parts by mass of water to obtain a formaldehyde scavenger of Comparative Example 3.

[Manufacture of building materials (plywood)]
Example 4
A melamine-urea copolymer resin is applied to one side of a 300 mm square lauan material with a roll coater so as to be 20 g / m ^2, and then an uncoated lauan material is layered thereon and applied for 5 minutes with a 135 ° C. press. The plywood (building material) was obtained by heating with pressure and further curing by heating in a circulating hot air oven at 120 ° C. for 60 minutes. The plywood thus obtained was sprayed with the formaldehyde scavenger of Example 1 on 5 surfaces excluding the back surface (adhesive surface) of the lauan material so as to be 12 g / m ^2, and the building material of Example 4 was applied. Obtained.

(Example 5)
In Example 4, the building material of Example 5 was obtained in the same manner as in Example 4 except that the formaldehyde scavenger of Example 2 was used instead of the formaldehyde scavenger of Example 1.

( Reference Example 2 )
In Example 4, the building material of Reference Example 2 was obtained in the same manner as in Example 4 except that the formaldehyde scavenger of Reference Example 1 was used instead of the formaldehyde scavenger of Example 1 .

(Comparative Example 4)
In Example 4, the building material of Comparative Example 4 was obtained in the same manner as Example 4 except that no formaldehyde scavenger was used.

(Comparative Example 5)
In Example 4, Example 4 was used except that the formaldehyde scavenger of Comparative Example 2 was used instead of the formaldehyde scavenger of Example 1 and the formaldehyde scavenger was applied, followed by drying in a circulating hot air oven at 80 ° C. for 20 minutes. In the same manner, a building material of Comparative Example 5 was obtained.

(Comparative Example 6)
In Example 4, the building material of Comparative Example 6 was obtained in the same manner as in Example 4 except that the formaldehyde scavenger of Comparative Example 3 was used instead of the formaldehyde scavenger of Example 1.

<Evaluation of formaldehyde emission from building materials>
The building materials (plywood) of Examples 4 to 5, Reference Example 2 and Comparative Examples 4 to 6 were cut as test pieces so that the total surface area was 1800 cm ^2, and the desiccator method according to JIS A 1460 was used. The formaldehyde emission was measured. The results are summarized in Table 1.

From the above results, it can be confirmed that the amount of formaldehyde released can be suppressed by applying the formaldehyde scavenger. In particular, the building materials (plywood) of Examples 4 to 5 obtained by attaching the formaldehyde scavenger of the present invention are Comparative Examples 5 obtained by attaching the formaldehyde scavengers of Comparative Examples 2 and 3. The formaldehyde emission was lower than the building materials (plywood) of No.6.

[Manufacture of building materials (inorganic fiber sound insulation)]
(Example 7)
Glass wool is used as the inorganic fiber, and 0.2 part by weight of aminosilane and 1 part by weight of ammonium sulfate as a curing catalyst are added to 100 parts by weight of a mixture in which the resol type phenol resin and urea resin are 70:30 as the binder. The binder adhering amount is applied to glass wool so that the binder adhesion amount is 9.5% by mass based on the mass of the inorganic fiber heat insulating sound absorbing material, and the inorganic fiber heat insulating sound absorbing material having a thickness of 25 mm and a density of 96 kg / m ³ is obtained. Obtained.

The building material of Example 7 was obtained by spraying the formaldehyde scavenger of Example 1 to 4.8 g / m ² with respect to the inorganic fiber heat insulating sound absorbing material thus obtained.

(Example 8)
In Example 7, the building material of Example 8 was obtained in the same manner as in Example 7 except that the formaldehyde scavenger of Example 2 was used instead of the formaldehyde scavenger of Example 1.

( Reference Example 3 )
In Example 7, the building material of Reference Example 3 was obtained in the same manner as in Example 7 except that the formaldehyde scavenger of Reference Example 1 was used instead of the formaldehyde scavenger of Example 1 .

(Comparative Example 7)
In Example 7, the building material of Comparative Example 7 was obtained in the same manner as in Example 7 except that no formaldehyde scavenger was used.

(Comparative Example 8)
In Example 7, the building material of Comparative Example 8 was obtained in the same manner as in Example 7 except that the formaldehyde scavenger of Comparative Example 1 was used instead of the formaldehyde scavenger of Example 1.

(Comparative Example 9)
In Example 7, Example 7 was used except that the formaldehyde scavenger of Comparative Example 2 was used instead of the formaldehyde scavenger of Example 1 and the formaldehyde scavenger was added, followed by drying in a circulating hot air oven at 80 ° C. for 5 minutes. In the same manner, a building material of Comparative Example 9 was obtained.

(Comparative Example 10)
In Example 7, Example 7 was used except that the formaldehyde scavenger of Comparative Example 3 was used instead of the formaldehyde scavenger of Example 1 and the formaldehyde scavenger was applied, followed by drying in a circulating hot air oven at 80 ° C. for 5 minutes. In the same manner, a building material of Comparative Example 10 was obtained.

(Comparative Example 11)
In Example 7, the building material of Comparative Example 11 was obtained in the same manner as in Example 7 except that the formaldehyde scavenger of Comparative Example 2 was used instead of the formaldehyde scavenger of Example 1.

<Evaluation of formaldehyde emission from building materials>
In accordance with JIS A 1901, Examples 7 to 8, Reference Example 3 and Comparative Examples 7 to 11 were obtained by cutting the building material (inorganic fiber heat-absorbing sound-absorbing material) so as to have a total surface area of 440 cm ^2. In addition, the formaldehyde emission rate after 1 day, 3 days, 7 days, 10 days, 14 days, and 21 days was measured by the small chamber method. The results are summarized in Table 2.

  From the above results, it can be confirmed that the emission of formaldehyde can be suppressed by applying the formaldehyde scavenger.

  That is, the formaldehyde emission rate of the building material (inorganic fiber heat insulating sound absorbing material) of Comparative Example 7 to which no formaldehyde scavenger is added is high immediately after the start of measurement, but decreases with time. Moreover, although the formaldehyde emission rate of the building materials (inorganic fiber heat insulating sound absorbing material) of Comparative Examples 8 to 11 is relatively lower than that of Comparative Example 7, it does not decrease with the passage of time, but increases and decreases were observed. . This is considered to be due to the effects of the formaldehyde scavengers of Comparative Examples 1 to 3 being adsorbed / desorbed on formaldehyde depending on the environmental conditions, or the diffusion of formaldehyde from the binder side due to moisture.

On the other hand, in the building materials of Examples 7 to 8 (inorganic fiber heat-absorbing sound-absorbing material) to which the formaldehyde scavenger of Examples 1 and 2 was applied, the increase and decrease did not occur with the passage of time, and the diffusion rate was 4 μg / m ² · It was less than h, and it was in the level corresponding to F ☆☆☆☆ even in the ranking by formaldehyde emission of the Building Standard Law.

  Since the formaldehyde scavenger of the present invention has a high formaldehyde scavenging effect even in a small amount of application and can maintain the effect over a long period of time, for example, a plywood using an aldehyde condensable thermosetting resin, an inorganic fiber heat insulating sound absorbing material, etc. By applying it to various building materials, it is possible to suppress the emission of formaldehyde, which causes damage to the living environment, and provide a comfortable living environment.

Claims (6)

It is obtained by mixing a polyamidoamine having a total amine value of 100 mgKOH / g or more and a solubility in water of less than 20 g / liter at 25 ° C. and a polyol having two or more hydroxyl groups that are liquid at 25 ° C. A formaldehyde scavenger, which is a composition obtained.   The formaldehyde scavenger according to claim 1, wherein the polyamidoamine is a condensate of an alkylene polyamine having two or more amino groups in the molecule and an aliphatic dicarboxylic acid having 6 or more carbon atoms.   The formaldehyde scavenger according to claim 1 or 2, wherein the polyol is an alkylene diol or a polyoxyalkylene diol.   The composition according to claim 1, wherein the composition is a composition obtained by mixing the polyamidoamine and the polyol such that the polyamidoamine / polyol is 5/95 to 30/70 by mass ratio. The formaldehyde scavenger according to any one of the above. The formaldehyde scavenger according to any one of claims 1 to 4 is added to the building material obtained by molding and curing a binder whose main component is an aldehyde-condensable thermosetting resin, and the surface area of the building material. On the other hand, the building material which carried out the formaldehyde emission suppression process characterized by making 1-20 g / m < ² > adhere by solid content.   The building material according to claim 5, wherein the building material is an inorganic fiber heat-absorbing sound absorbing material or plywood.