JPH11114041A - Aldehyde adsorbent, its use and its use - Google Patents

Abstract

(57) [Problem] To provide an aldehyde adsorbent which is extremely excellent in reducing formaldehyde. An aldehyde adsorbent comprising a saturated polyester resin containing an acetoacetyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aldehyde adsorbent, and more particularly to an aldehyde adsorbent comprising an acetoacetyl group-containing saturated polyester resin which adsorbs formaldehyde generated from various substrates.

[0002]

2. Description of the Related Art In recent years, formaldehyde has been used in a large amount as a raw material for producing low-molecular-weight synthetic materials and high-molecular resins. And resins obtained from these, such as phenol-formaldehyde resin, melamine-formaldehyde resin, urea-formaldehyde resin, guanamine-
Formaldehyde resins and the like are used in a wide range of applications such as adhesive processing, molding processing, paper processing, fiber processing, paints, decorative boards and the like. However, when manufacturing or processing such a resin, the problem that formaldehyde often escapes in the atmosphere, albeit slightly, to cause an irritating odor, and furthermore, various processing obtained using such a resin. Products also tend to produce formaldehyde, which is a problem.

[0003] Wood that does not use an adhesive or the like made of the above-mentioned resin also contains formaldehyde, and it is known that a trace amount of formaldehyde is also emitted into the air from such wood. Formaldehyde is harmful to the human body, and if it is present in air at 10 ppm or more, it cannot withstand the irritating odor, and it is closely related to processed products and daily life, such as building materials, equipment, clothing, automobiles, sanitary materials, miscellaneous goods, There is a strong demand for a method for reducing formaldehyde generated from foods and the like.

[0004] As one of such measures, use of a formaldehyde scavenger is widely used. As a formaldehyde scavenger, conventionally, urea, thiourea, ethylene urea, dicyandiamide, glyoxal monourethane, and the like are known. There is a method of attaching a capturing agent by spraying or the like.

[0005]

However, as a result of a detailed study by the present inventors, it has been found that the above method is not yet satisfactory in terms of formaldehyde adsorption ability. Therefore, an object of the present invention is to provide an aldehyde adsorbent that efficiently reduces formaldehyde.

[0006]

In view of the above circumstances, the present inventor has conducted intensive studies and found that an aldehyde adsorbent comprising an acetoacetyl group-containing saturated polyester resin can reduce aldehydes such as formaldehyde. It was found that the present invention exhibited excellent effects, and the present invention was completed. In the present invention, it is preferable to blend a curing agent and / or a standing stabilizer in the acetoacetyl group-containing saturated polyester resin.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. The most characteristic feature of the adsorbent of the present invention is that it comprises a saturated polyester resin containing an acetoacetyl group. The saturated polyester resin containing an acetoacetyl group is produced, for example, as follows.

(1) A method in which a diketene is added to a functional group such as a hydroxyl group or an amino group in the polyester after the polyester polycondensation. This reaction may be without catalyst,
It is desirable to carry out the reaction in the presence of a catalyst of a tertiary amine, an acid (such as sulfuric acid), or a basic salt (such as sodium acetate). (2) A method in which a diketene is added to a monomer before polyester polycondensation and then polycondensed to obtain a polyester. (3) A method in which the diketene is subjected to an addition reaction in the middle of the polyester polycondensation, and then the polycondensation is further continued.

(4) A method in which, after the polyester polycondensation, an acetoacetate such as methyl acetoacetate or ethyl acetoacetate is introduced into a functional group such as a hydroxyl group or an ester group in the polyester by a transesterification reaction. This reaction is preferably performed in the presence of a catalyst such as calcium acetate, zinc acetate and lead acetate. (5) A method of transesterifying a monomer before polyester polycondensation with an acetoacetate ester and then performing polycondensation to obtain a polyester. (6) A method in which acetoacetate is introduced by a transesterification reaction in the middle of the polyester polycondensation, and then the polycondensation is further continued. In addition, even if it is a method other than said (1)-(6), what is necessary is just to introduce | transduce an acetoacetyl group into a saturated polyester as a result.

The saturated polyester in the present invention is a polymer obtained by a condensation reaction between a polyhydric alcohol and a polybasic acid. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene. Glycol,
Trimethylene glycol, butylene glycol (1,
3), butylene glycol (2,3), tetramethylene glycol, bisphenol dioxyethyl ether,
Bihydric alcohols such as bisphenoldioxypropyl ether, neopentyl glycol, butenediol (1,4), and trivalents such as glycerin, trimethylolpropane, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, and sorbitol One or more of the above alcohols are used.

The polybasic acids include phthalic acid, isophthalic acid, terephthalic acid, 3,6-endomethylenetetrahydrophthalic anhydride, tetrahydrophthalic acid, tetrachlorophthalic anhydride, 3,6-endodichloromethylenetetrachlorophthalic acid, Succinic acid, adipic acid, sebacic acid,
One or more unsaturated polybasic acids such as terpene-maleic anhydride adduct, rosin-maleic anhydride adduct, etc., itaconic acid, mesaconic acid, citraconic acid, citraconic anhydride, chlorinated maleic acid, etc. Two or more are used.
In addition, trivalent or higher valent acids such as pyromellitic acid, pyromellitic anhydride, and trimellitic acid can also be used.

In addition to polyhydric alcohols and polybasic acids, denaturing substances such as allyl alcohol and other monohydric alcohols, oils and fats, oils and fatty acids, and other resins used for denaturing alkyds (acrylic denaturation) can also be used.

In order to introduce an acetoacetyl group into a saturated polyester, as described above, diketene must be reacted with the raw material component or the resulting polyester, so that at least a part thereof is a trihydric or higher polyhydric alcohol or polyhydric alcohol. It is preferred to use a basic acid. However, an acetoacetyl group can be introduced into a terminal or a side chain using only a dihydric alcohol and a dihydric acid.

The content of the acetoacetyl group in the saturated polyester resin is suitably 0.01 to 40% by weight, preferably 1 to 20% by weight, and more preferably 3 to 15% by weight. When the content is less than 0.01% by weight, the aldehyde adsorption ability is poor, and when it exceeds 40% by weight, the storage stability of the resin is poor, which is not preferable.

In the present invention, the acetoacetyl group-containing saturated polyester resin as described above is very effective as an aldehyde adsorbent for a formaldehyde-containing resin or a substrate, and exhibits an excellent effect of reducing formaldehyde. It is.

In the present invention, the aldehyde adsorbent comprising the acetoacetyl group-containing saturated polyester resin is added to a conventionally known formaldehyde adsorbent such as urea.
It is also possible to use thiourea, ethylene urea, dicyandiamide, glyoxal monourethane and the like in combination. When the known formaldehyde adsorbent is used in combination, it is appropriate to add 5 to 50 parts by weight, preferably 5 to 25 parts by weight, per 100 parts by weight of the acetoacetyl group-containing saturated polyester resin.

The aldehyde adsorbent of the present invention is prepared by, for example, dissolving the above acetoacetyl group-containing saturated polyester resin in water or an organic solvent such as toluene, xylene, ethyl acetate, isopropyl alcohol or the like to form a liquid or powder. Alternatively, the emulsion may be subjected to emulsion polymerization to form an emulsion, or formed into a sheet or film by casting and extrusion molding, and put into practical use.

In using the aldehyde adsorbent of the present invention, the aldehyde adsorbent may be used as it is in paints and adhesives, or may be added to an object such as an adhesive or other formaldehyde-containing resin or compound. Formaldehyde can be reduced by forming a processed product or by applying or impregnating a substrate such as paper, fiber (woven or nonwoven fabric), or wood (including those coated with an adhesive or a paint).

In the present invention, it is preferable that a curing agent is further added to the acetoacetyl group-containing saturated polyester resin. Examples of the curing agent include a melamine resin, an isocyanate compound, a metal chelate compound, and an organic metal. Examples include compounds, hydrazide compounds, epoxy compounds, imine compounds, and unsaturated compounds.
Among them, melamine resins and isocyanate compounds are particularly preferred. The amount is 0.1 to 1 part by weight per 100 parts by weight of the acetoacetyl group-containing saturated polyester resin.
00 parts by weight, preferably 0.1 to 70 parts by weight, is suitable.

In the present invention, it is preferable to further add a standing stabilizer to the acetoacetyl group-containing saturated polyester resin. Examples of the standing stabilizer include acetylacetone, acetoacetate (such as ethyl acetoacetate), and the like. Examples thereof include acetic anhydride and sodium hydrogen phosphate. The amount is 1 to 10 parts by weight, based on 100 parts by weight of the acetoacetyl group-containing saturated polyester resin.
Preferably, 1 to 5 parts by weight is appropriate.

Specific examples of the use of the present invention include: a) coating the adsorbent of the present invention on interior / exterior materials of buildings, wood, paper, plastic, and metal; adhesives and pressure-sensitive adhesives; Lay the non-woven fabric impregnated with the agent under the flooring material,
C) Adhesive used for bonding wood, paper, etc., mixed with paint, etc., and used as it is as adhesive or paint.
Use as a rug for furniture drawers or closets,
E) used for packaging of textile products; f) impregnated in paper and affixed to the decorative surface of decorative plywood; g) placing the molded article containing the adsorbent of the present invention in a refrigerator or freezer; )) In combination with activated carbon and deodorant, g) air purifier,
These are used by being contained in a filter such as a cooler or a heater, and (c) mixing the adsorbent of the present invention into a fragrance in a room or the like to form a molded article and using it as a fragrance or deodorant. However, the present invention is not limited to this.

Thus, the aldehyde adsorbent of the present invention can be used in any form, and exhibits an extremely excellent effect in reducing formaldehyde generated from an object such as a resin or a compound containing formaldehyde or a base material. It is very useful for applications as paints and adhesives, especially woodworking paints and adhesives.

[0023]

The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” mean on a weight basis unless otherwise specified.

Example 1 [Saturated polyester resin containing acetoacetyl group (A-
Production of 1)] A rectification column in a 2 L four-necked round bottom flask,
A stir bar and a thermometer were attached, and 201.0 g of trimethylolpropane, 35.4 g of 1,6-hexanediol,
352.8 g of isophthalic acid was charged, and heating was started under a nitrogen stream. Water began to distill when the internal temperature exceeded 210 ° C. The polycondensation reaction was performed for 4 hours while maintaining the internal temperature at 220 to 230 ° C (95 to 103 ° C at the top of each rectification column).
The amount of distilled water was 52 g.

Subsequently, the internal temperature was lowered to 120 ° C., 208.8 g of methyl acetoacetate and 1.04 g of zinc acetate as a transesterification catalyst were added, and the mixture was heated again. When the internal temperature exceeded 125 ° C., methanol began to distill. Keep the internal temperature at 130-135 ° C (the rectification tower top temperature is 60-67
℃), transesterification reaction and polycondensation reaction were performed for 2 hours. The total amount of methanol distilled was 36.7 g. After the heating was stopped, 300 g of butyl acetate was added and diluted in the course of cooling to obtain a resin solution (concentration: 60%).

The above resin solution was applied to both sides of the particle board and dried (the applied amount is 100 μm in thickness after drying). After leaving the particle board at room temperature for one week, the amount of formaldehyde was measured by the following measurement method. The result was 0 ppm.

(Measurement method) In accordance with JIS A 5908, 300 m
Place a crystal dish with a diameter of 12 cm and a height of 6 cm containing ml of distilled water, place a predetermined number of test pieces on the crystal dish using a support bracket, and leave at 20 ± 1 ° C for 24 hours to release. The formaldehyde is absorbed in distilled water. The concentration of formaldehyde in the test solution is colorimetrically determined by an acetylacetone method using a photoelectric spectrophotometer or a photoelectric colorimeter.

Comparative Example 1 The same treatment as in Example 1 was carried out except that a saturated polyester resin containing no acetoacetyl group was used, and the amount of formaldehyde was measured in the same manner as in Example 1. The result was 35 ppm.

Example 2 [Saturated polyester resin containing acetoacetyl group (A-
Production of 2)] Trimethylolpropane 22.7 in a reaction vessel
g, neopentyl glycol 23.8 g, adipic acid 19.8 g, itaconic acid 33.7 g, toluene 12 g and isobutyl acetate 25 g, and the system was replaced with nitrogen.
By reacting at a temperature of 190 to 210 ° C. for 6 hours,
An oil-free polyester having a hydroxyl value of 95 was obtained. To the resulting resin solution, 19 g of diketene was dropped at 90 ° C. over 2 hours using triethylenediamine as a catalyst to obtain a saturated polyester resin solution in which hydroxyl groups were acetoacetylated. After dilution with toluene, a resin solution having a concentration of 60% was obtained.

The above resin solution was applied to both surfaces of the particle board and dried (the applied amount is 100 μm in thickness after drying). After leaving the particle board at room temperature for one week, the amount of formaldehyde was measured in the same manner as in Example 1.
The result was 0 ppm.

Comparative Example 2 The same treatment as in Example 2 was carried out except that a saturated polyester resin containing no acetoacetyl group was used.
The amount of formaldehyde was measured in the same manner as above. The result was 38 ppm.

Example 3 In Example 1, a solution of the acetoacetyl group-containing saturated polyester resin (A-1) was further added with urea (A-1).
The same treatment is performed except that 10 parts are blended with respect to 0 parts.
The amount of formaldehyde was measured in the same manner as above. The result was 0 ppm.

Comparative Example 3 The procedure of Example 3 was repeated except that the acetoacetyl group-containing saturated polyester resin (A-1) was not used and only urea was used, and the amount of formaldehyde was measured in the same manner as above. . The result was 20 ppm.

Example 4 In Example 1, acetylacetone was added to the solution of the acetoacetyl group-containing polyester resin (A-1).
1) The same treatment was carried out except that 3 parts were added to 100 parts, and the amount of formaldehyde was measured in the same manner as above. The result was 0 ppm.

[0035]

The aldehyde adsorbent of the present invention is in the form of a liquid, powder, sheet, film, fibrous, or other resin or compound, a molded product contained in a substrate, a paint, an adhesive, an adhesive. Since it can be used in any form, such as an agent, and is made of a saturated polyester resin containing an acetoacetyl group, it exhibits a very excellent effect in reducing formaldehyde generated from an object containing formaldehyde or a substrate.

Claims (12)

[Claims] 1. An aldehyde adsorbent comprising a saturated polyester resin containing an acetoacetyl group. 2. The aldehyde adsorbent according to claim 1, further comprising a curing agent. 3. The aldehyde adsorbent according to claim 1, further comprising at least one compound selected from urea, thiourea, ethylene urea, dicyandiamide, and glyoxal monourethane. 4. The aldehyde adsorbent according to claim 1, further comprising a standing stabilizer. 5. The aldehyde adsorbent according to claim 1, wherein the aldehyde adsorbent is formed in a liquid, powder, sheet, film, or fiber shape. 6. A paint comprising the aldehyde adsorbent according to claim 1. 7. An adhesive comprising the aldehyde adsorbent according to claim 1. 8. A molded article comprising the aldehyde adsorbent according to claim 1. 9. A deodorant comprising the aldehyde adsorbent according to claim 1. Description: 10. A method for using an aldehyde adsorbent, comprising adding the aldehyde adsorbent according to any one of claims 1 to 5 to an object containing formaldehyde. 11. A method for using an aldehyde adsorbent, which comprises applying or impregnating the aldehyde adsorbent according to claim 1 to a substrate containing formaldehyde. 12. A method for using an aldehyde adsorbent, which comprises applying or impregnating the aldehyde adsorbent according to claim 1 to a woven or nonwoven fabric containing formaldehyde.