JPH11197502A - Aldehyde adsorbent, its use and using method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently decrease formaldehyde by preparing an adsorbent from an unsatd. polyester resin containing acetoacetyl groups and compounding a hardening agent and/or storage stabilizer. SOLUTION: This adsorbent consists of an unsatd. polyester resin containing acetoacetyl groups. When the unsatd. polyester resin containing acetoacryl groups is used as a hardening type resin compsn. which is hardened with active energy rays, a radical-producing photopolymn. initiator is used together. When using as a hardening resin compsn. which is hardened at normal temp. or by heating, a radical producing agent by heat is used instead of a radical-producing photopolymn. initiator. Further, a storage stabilizer is preferably compounded to the unsatd. polyester resin containing acetoacetyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aldehyde adsorbent, and more particularly to an aldehyde adsorbent comprising an acetoacetyl group-containing unsaturated 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, urea, thiourea, ethylene urea, dicyandiamide, glyoxal monourethane and the like are conventionally known, and are treated in the same bath as the above-mentioned formaldehyde-containing resin, or after processing with formaldehyde-containing resin, formaldehyde 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]

Accordingly, the present inventor has conducted intensive studies in view of such circumstances, and as a result, has found that an aldehyde adsorbent comprising an acetoacetyl group-containing unsaturated polyester resin reduces aldehydes such as formaldehyde. The present inventors have found that the present invention has excellent effects, and have completed the present invention. In the present invention, it is preferable to blend a curing agent and / or a standing stabilizer in the acetoacetyl group-containing unsaturated 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 is composed of an unsaturated polyester resin containing an acetoacetyl group. The unsaturated 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 unsaturated polyester as a result.

The unsaturated polyester in the present invention is:
a polymer obtained by a condensation reaction between an α, β-unsaturated polybasic acid or an anhydride thereof (a saturated acid is used in combination if necessary) and a polyhydric alcohol; Examples of the acid or its anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, mesaconic acid, and the like. Examples of the acid include phthalic anhydride, phthalic acid, terephthalic acid, isophthalic acid, heptic acid, adipic acid, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid, and anhydride. Pyromellitic acid,
6-methyl-4-cyclohexene-1,2,3 tricarboxylic anhydride and the like.

The polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 6-hexane glycol, 1,9-nonane glycol, neopentyl glycol, trimethylolpropane, methylolethane, pentaerythritol, glycerin, sorbitol, bisphenol A alkylene oxide adduct,
Hydrogenated bisphenol A, polypropylene glycol, polyethylene glycol, polytetramethylene glycol, 2-ethyl-1,3-hexanediol, 2,2,4
-Trimethyl-1,3-pentanediol, trimethylolethane, cyclohexanedimethanol and the like, and one or more of these are appropriately selected.

In addition to the above-mentioned polybasic acids and polyhydric alcohols, denaturing substances such as allyl alcohol, other monohydric alcohols, oils and fats, oils and fatty acids, and other resins used for denaturing alkyds (acrylic modification) may be used. it can.

In order to introduce an acetoacetyl group into the unsaturated 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 Preferably, a polybasic acid is used. 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 unsaturated polyester resin is 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 unsaturated 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. You do it.

In the present invention, a conventionally known formaldehyde adsorbent such as urea, thiourea, ethylene urea, dicyandiamide, glyoxal monourethane, etc. is used in combination with the aldehyde adsorbent comprising the acetoacetyl group-containing unsaturated polyester resin. It is also possible. When the known formaldehyde adsorbent is used in combination, the acetoacetyl group-containing unsaturated polyester resin 100
It is appropriate to add 5 to 50 parts by weight, preferably 5 to 25 parts by weight with respect to parts by weight.

The aldehyde adsorbent of the present invention can be prepared by dissolving the acetoacetyl group-containing unsaturated 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. Or emulsion polymerization by emulsion polymerization,
Furthermore, it can be formed into a sheet or film by casting and extrusion, or can be formed into a fiber and put to practical use.

In the use of the aldehyde adsorbent of the present invention, the aldehyde adsorbent may be used as it is in paints and adhesives (adhesives), or may be an object such as a resin or compound containing formaldehyde such as an adhesive. To form processed products, or to apply or impregnate substrates such as paper, fiber (woven or non-woven fabric) or wood (including those coated with adhesives or paints) to reduce formaldehyde be able to.

In the use described above, the acetoacetyl group-containing unsaturated polyester resin is generally cured by an active energy ray or heating, and in some cases, by standing at room temperature. When used as a curable resin composition, it is necessary to further use a radical-generating photopolymerization initiator, and the initiator is not particularly limited as long as it generates a radical by the action of light. Specifically, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylenephenyl) ) -2-Hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2 Hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) - phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether,
Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid,
Methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4 '
-Methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone,
2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-
Ethylanthraquinone, 4 ', 4 "-diethylisophthalophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxy And benzyl, 9,10-phenanthrenequinone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and the like, and triethanolamine, triisopropanolamine as auxiliary agents thereof. 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diemethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy) Ethyl, 4-dimethylamino benzo It is also possible to use isoamyl acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like in combination. Among them, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenyl Propan-1-one is preferably used.

The amount of the photopolymerization initiator is preferably 1 to 20 parts by weight, more preferably 2 to 1 part by weight, based on 100 parts by weight of the acetoacetyl group-containing unsaturated polyester resin.
0 parts by weight is preferred. When the amount is too small, the curability is slow. On the contrary, when the amount is too large, the curability is not improved and it is useless.

The method of curing such a curable resin composition is not particularly limited as long as it is a method of activating the above-mentioned radical-generating photopolymerization initiator, and it is far ultraviolet, ultraviolet, near ultraviolet, and red. An external light beam, X-ray, a method of irradiating an electromagnetic wave such as a gamma ray or an electron beam, a proton beam, an activation energy ray such as a neutron beam and curing the same, and the like are mentioned. In view of the price and the like, a curing method using ultraviolet irradiation is advantageous, and the ultraviolet light is 150 to 450 nm.
The method mainly uses light in a wavelength range and includes a method of irradiating with a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, or the like.

When the above-mentioned acetoacetyl group-containing unsaturated polyester resin is used as a curable resin composition which cures at room temperature or by heating, the radical-generating photopolymerization initiator is replaced with the radical-generating photopolymerization initiator. An agent may be used. Such radical generators include methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, t-butyl perbenzoate, and the like. It is also possible to use a curing agent such as cobalt oxide, manganese octenoate, manganese naphthenate, and various amine compounds in combination, and preferably methyl methyl ketone peroxide and cobalt octenoate are used in combination.

The amount of the radical generator is preferably 1 to 20 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the acetoacetyl group-containing unsaturated polyester resin.
10 parts by weight are preferred. When the amount is too small, the curability is slow. On the contrary, when the amount is too large, the curability is not improved and it is useless.

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

Specific examples of the use of the aldehyde adsorbent comprising the acetoacetyl group-containing unsaturated polyester resin of the present invention include: a) The adsorbent of the present invention is used for building interior and exterior materials, wood, paper, plastic, and metal. A) A nonwoven fabric impregnated with the adsorbent of the present invention is laid under a flooring material. C) An adhesive or paint used for bonding wood, paper, etc. Mix and use as an adhesive or paint as it is; d) Use as a rug such as drawer or push-in furniture; e) Use for packaging of textiles; f) Impregnate paper and paste on the decorative surface of decorative plywood A) A molded article containing the adsorbent of the present invention is placed in a refrigerator or a freezer. C) A deodorant is used in combination with activated carbon in the above-mentioned b). K) Air purifiers, coolers, heaters, etc. Contained in filter It was used, co) mixing the adsorbent of the present invention in the aromatic agent such as indoor use as fragrances or deodorant to the molded body, but and the like, but is not limited thereto.

Thus, the aldehyde adsorbent of the present invention can be used in any form, and exhibits an extremely excellent effect on reducing formaldehyde generated from an object such as a resin or a compound containing formaldehyde or a base material. Among paints and adhesives (adhesives), they are very useful for applications as woodwork paints and adhesives.

[0027]

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 [Acetacetyl group-containing unsaturated polyester resin (A
-1) Production] 1 mol of maleic anhydride was placed in a four-necked flask equipped with a stirrer, a gas inlet tube, a thermometer and a reflux condenser.
0.4 mol of diethylene glycol, 0.2 mol of trimethylolpropane and 0.2% of hydroquinone based on the total of these were added, and the mixture was added at 150 ° C. in a nitrogen gas stream at 1.degree.
The reaction was carried out for 5 hours, to which 0.4 mol of ethylene glycol, 0.15 mol of diethylene glycol and 5% of xylene for reflux were added, and after the temperature was slowly raised to 150 to 180 ° C., the reaction was further carried out for 2 hours. Subsequently, the internal temperature was lowered to 120 ° C., 1 mol of methyl acetoacetate and 0.1% of zinc acetate as a transesterification catalyst were added, and the mixture was heated again. When the internal temperature exceeds 125 ° C., methanol starts to be distilled off, and the internal temperature is kept at 130 to 135 ° C., transesterification reaction and polycondensation reaction are performed for 2 hours, and the acetoacetyl group-containing unsaturated polyester resin (A-1) I got

The above acetoacetyl group-containing unsaturated polyester resin (A-1) was diluted with a styrene monomer to obtain a 65% solution, and 100 parts of the resin solution was added with benzyl dimethyl ketal as a radical-generating photopolymerization initiator. 5 parts (Circa Geigy; Irgacure 651) were added to obtain an active energy ray-curable resin composition. The resulting curable resin composition was dried on a particle board (initial formaldehyde content: 82 ppm) to a thickness of 100 μm after drying.
It was applied and cured by repeatedly passing it at a height of 15 cm under a high-pressure mercury lamp of 80 W / cm at a speed of 5 m / min. The same processing was performed on the back surface. After leaving the particle board at room temperature for one week, the amount of formaldehyde was measured by the following measurement method. The result is 0 ppm
Met.

(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 an unsaturated polyester resin containing no acetoacetyl group was used.
The amount of formaldehyde was measured in the same manner as in Example 1. The result was 48 ppm.

Example 2 [Acetacetyl group-containing unsaturated polyester resin (A
Production of -2)] In Example 1, diketen was used in an amount of 20% of the amount of the ester component charged at a temperature of 90 ° C. using triethylenediamine as a catalyst instead of adding methyl acetoacetate.
For 2 hours to obtain an unsaturated polyester (A-2) in which a hydroxyl group was acetoacetylated, and an active energy ray-curable resin composition was obtained in the same manner as in Example 1.

The curable resin composition was applied to a particle board in the same manner as in Example 1, was cured by irradiation with active energy rays, and the amount of formaldehyde after one week of standing was measured in the same manner as in Example 1. The result was 0 ppm.

Comparative Example 2 The procedure of Example 2 was repeated, except that an unsaturated polyester resin containing no acetoacetyl group was used, and the amount of formaldehyde was measured in the same manner as described above. The result was 34 ppm.

Example 3 The procedure of Example 1 was repeated, except that urea was further added to the styrene monomer solution of the acetoacetyl group-containing unsaturated polyester resin (A-1) in an amount of 10 parts per 100 parts of (A-1). And the amount of formaldehyde was measured in the same manner as above. The result was 0 ppm.

Comparative Example 3 In Example 3, the styrene monomer solution of the acetoacetyl group-containing unsaturated polyester resin (A-1) was not contained, and only urea was applied to the front and back of the particle board. It was measured. The result was 20 ppm.

Example 4 The procedure of Example 1 was repeated, except that the styrene monomer solution of the acetoacetyl group-containing unsaturated polyester resin (A-1) was further mixed with 3 parts of acetylacetone per 100 parts of (A-1). And the amount of formaldehyde was measured in the same manner as above. The result was 0 ppm.

[0038]

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 an unsaturated polyester resin containing an acetoacetyl group, it has a very excellent effect in reducing formaldehyde generated from an object containing formaldehyde or a base material.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/21 C08K 5/21 5/315 5/315 5/405 5/405 C08L 67/06 C08L 67/06 C09D 5/00 C09D 5/00 Z 167/06 167/06 C09J 11/08 C09J 11/08 167/06 167/06

Claims (12)

[Claims] 1. An aldehyde adsorbent comprising an acetoacetyl group-containing unsaturated polyester resin. 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 the group consisting of 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.