JPH11165379A - Aldehyde absorption film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently reduce a formaldehyde by laminating a thermoplastic resin film and an acetoacetyl group-containing polymer compound layer. SOLUTION: An acetoacetyl group-containing polymer compound layer is laminated on one or both side surfaces of a thermoplastic resin film (particularly preferably a polyvinyl alcohol film). However, in the case of laminating it only on the one side surface, a base material such as a fiber product or the like is disposed at the acetoacetyl group-containing polymer compound layer laminated surface side. Thus, an object containing a formaldehyde or a formaldehyde generated from the base material is reduced, and further occurrence of a bleeding or the like can be prevented without generating a migration of the formaldehyde.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for absorbing 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 therefrom, for example, phenol-formaldehyde resin, melamine-formaldehyde resin, urea-formaldehyde resin, guanamine-formaldehyde resin, etc.
It is used in a wide variety of applications such as fiber processing, paints, decorative boards, etc.

[0003] However, various processed products obtained by using such a resin tend to generate formaldehyde, which causes a problem of escaping into the atmosphere and causing an irritating odor. Because it is often used, it may remain in textiles and cause skin damage. In particular, the dangers of shirts, polo shirts, and the like cannot be overlooked because they directly touch the skin. or,
Formaldehyde is a substance that is very easy to transfer, and formaldehyde remaining on plywood such as furniture may contaminate textiles and the like that are not processed with formaldehyde.

As one of the countermeasures, use of a formaldehyde scavenger is widely used, and a film containing formaldehyde is trapped on a film containing formaldehyde by known aldehydes such as urea, thiourea, ethylene urea, dicyandiamide, and glyoxal monourein. There is a method of adding an agent. Further, it has been proposed to use a film made of polyvinyl alcohol containing a compound having a -NH- bond in the molecule (Japanese Patent Application Laid-Open No. 9-100382).

[0005]

However, in the method of adding a known formaldehyde scavenger, problems such as bleeding of low molecular weight compounds reacting with aldehyde and insufficient deodorizing ability remain. Also, JP-A-9-
In the technology described in JP 1003822, the ability to deodorize formaldehyde, the ability to prevent formaldehyde migration,
It turned out that the retention was not yet satisfactory. In view of the foregoing, an object of the present invention is to provide an aldehyde-absorbing film capable of efficiently reducing formaldehyde without causing problems such as bleeding in such a background.

[0006]

The inventors of the present invention have conducted intensive studies in view of such circumstances, and as a result, have found that an aldehyde-absorbing film formed by laminating a thermoplastic resin film and an acetoacetyl group-containing polymer compound layer is obtained. The inventors have found that the object of the present invention is met, and have completed the present invention. In the present invention, the thermoplastic resin film is preferably a polyvinyl alcohol-based film in terms of gas barrier properties, flexibility, non-charging properties, and the like, and the acetoacetyl group-containing polymer compound is an acetoacetyl group-containing polyvinyl compound. It is preferably an alcohol-based resin.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. As the thermoplastic resin film used in the present invention, without particular limitation, polyethylene, polypropylene and polyolefin-based films such as copolymers thereof, vinyl chloride and its copolymer film, cellulose-based film, polyamide-based film, Polyester-based films and the like are mentioned, and polyvinyl alcohol-based films are particularly preferred from the viewpoints of gas barrier properties, flexibility, non-charging properties and the like, and excellent adhesion when laminated (especially when coated). The polyvinyl alcohol-based film is not particularly limited as long as it is made of a polyvinyl alcohol-based resin.

The polyvinyl alcohol resin is usually produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate. The polyvinyl alcohol resin is preferable, but the present invention is not limited to this. And a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability with vinyl acetate. Further, there may be mentioned so-called polyvinyl acetal resins such as polyvinyl butyral resins and polyvinyl formal resins obtained by reacting polyvinyl alcohol resins with aldehydes in the presence of an acid, and other polyvinyl alcohol-based resin derivatives.

Examples of such a monomer include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene and α-octadodecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, Unsaturated acids such as itaconic acid or salts thereof or mono- or dialkyl esters; acrylonitrile; nitriles such as methacrylonitrile; amides such as acrylamide and methacrylamide; ethylene sulfonic acid, allyl sulfonic acid; Olefin sulfonic acid or its salt, alkyl vinyl ethers, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethyldiallylammonium chloride, dimethylallylvinylketo , N- vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (meth)
Polyoxyalkylene (meth) allyl ethers such as allyl ether and polyoxypropylene (meth) allyl ether; polyoxyalkylene (meth) acrylates such as polyoxyethylene (meth) acrylate and polyoxypropylene (meth) acrylate; polyoxyethylene Polyoxyalkylene (meth) such as (meth) acrylamide and polyoxypropylene (meth) acrylamide
Acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester,
Examples thereof include saponified copolymers with polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, and the like.

The degree of polymerization of the polyvinyl alcohol resin is 3
00 to 30,000 is preferred, and especially 1000 to 3000
Is preferred. If the degree of polymerization is less than 300, the film strength becomes insufficient. If it exceeds 3,000, the viscosity becomes high depending on the film forming method, and the workability is undesirably reduced. The degree of saponification of the polyvinyl alcohol resin is 65.
To 100 mol%, preferably 90 to 100 mol%
Is preferred. If the saponification degree is less than 65 mol%, the formation of a cloud point will hinder film formation, and the film strength will be further reduced, which is not preferable. In particular, for applications requiring water resistance, a higher saponification degree is preferable because of higher crystallinity and water resistance.

The method for producing a polyvinyl alcohol-based film is not particularly limited, and is appropriately selected depending on the thickness of the film, the use of the film, and the purpose. Usually, a cast film-forming method from a solution, a dry film-forming method, a dry-wet method, A film forming method, a gel film forming method, a melt film forming method, or the like is used. As the solvent used at this time, water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, ethylene glycol, glycerin, diglycerin, hexafluoroisopropanol and the like are used alone or in combination.

[0012] The concentration of the polyvinyl alcohol resin at the time of film formation is 1 to 50% by weight, preferably 5 to 30% by weight.
It is performed in the range of 0 ° C. The thickness of the obtained polyvinyl alcohol-based film is 5 to 200 μm, preferably 25 to 200 μm.
100 μm is desired. Further, the polyvinyl alcohol-based film may be used without stretching or may be used after being uniaxially stretched, and is not particularly limited. In the case of a uniaxially stretched film, it is preferably, for example, 1.1 to 7 times, particularly preferably 3 to 5 times.

The acetoacetyl group-containing polymer compound layer used in the present invention is a layer composed of an acetoacetyl group-containing polymer compound. Although not particularly limited, for example, acetoacetyl group-containing polyvinyl alcohol resin, acetoacetyl group-containing acrylic resin,
Examples include an acetoacetyl group-containing unsaturated polyester resin, an acetoacetyl group-containing saturated polyester resin, an acetoacetyl group-containing urethane acrylic resin, and an acetoacetyl group-containing epoxy acrylic resin. A polyvinyl alcohol-based resin is exemplified.

The acetoacetyl group-containing polyvinyl alcohol resin will be described below. The acetoacetyl group-containing polyvinyl alcohol-based resin may be any of a method of reacting polyvinyl alcohol with diketene, a method of transesterifying polyvinyl alcohol by reacting with acetoacetate, and a method of copolymerizing vinyl acetate and vinyl acetoacetate. Although it may be produced by a method, it is preferably produced by a method in which polyvinyl alcohol and diketene are reacted because the production process is simple and a high-quality acetoacetyl group-containing polyvinyl alcohol-based resin can be obtained. As a method of reacting polyvinyl alcohol and diketene, polyvinyl alcohol and gaseous or liquid diketene may be directly reacted, or an organic acid is preliminarily adsorbed and occluded in polyvinyl alcohol, and then liquid or inert gas atmosphere. A method of spraying and reacting gaseous diketene or spraying and reacting a mixture of an organic acid and liquid diketene on polyvinyl alcohol is used.

[0015] As the above-mentioned polyvinyl alcohol, similarly to the above, polyvinyl alcohol or a derivative thereof obtained by saponifying a lower alcohol solution of polyvinyl acetate with a saponification catalyst such as an alkali, and further having the copolymerizability with vinyl acetate. A saponified product of a copolymer of a monomer and vinyl acetate is exemplified.

As a reaction device for containing an acetoacetyl group, any device that can be heated and has a stirrer is sufficient. For example, a kneader, a Henschel mixer, a ribbon blender, various other blenders, and a stirring and drying device can be used. The acetoacetyl group-containing polyvinyl alcohol-based resin obtained as described above has an average degree of polymerization of 100 to 4
000, preferably 300 to 3000, more preferably 250 to 2800, saponification degree 65 to 100 mol%, preferably 68 to 100 mol%, more preferably 70 to 10 mol%.
Desirably, it is 0 mol%. The acetoacetyl group content is 0.5 to 20 mol%, preferably 0.5 to 15 mol%.
It is desirable that the content be 2 mol%, more preferably 2 to 10 mol%. When the acetoacetyl group content is less than 0.5 mol%, the deodorizing ability of formaldehyde becomes insufficient. On the other hand, when it exceeds 20 mol%, the acetoacetyl group-containing polyvinyl alcohol-based resin becomes insoluble, which is not preferable.

In the present invention, if necessary, a phosphoric acid-based glass powder containing at least 2% by weight of a conventionally known deodorant such as phosphorus oxide or silver oxide in the acetoacetyl group-containing polymer compound, Diamines, polyalkylene diamines, ferric chloride, chromium chloride, manganese chloride, nickel chloride, copper chloride, iron chloride and the like can be contained. Among the known deodorants, phosphate glass powder,
When an alkylenediamine or a polyalkylenediamine is used in combination, 0.1 to 20 parts by weight, preferably 0.3 to 1 part by weight per 100 parts by weight of the acetoacetyl group-containing polymer compound.
It is appropriate to mix 5 parts by weight.

When a metal ion such as ferric chloride, chromium chloride, manganese chloride, nickel chloride, copper chloride, or iron chloride is added, the acetoacetyl group (and hydroxyl group) of the acetoacetyl group-containing polymer compound is added. It is suitable to mix 2 to 100 mol%, preferably 5 to 80 mol%. The metal ion forms a chelate with an acetoacetyl group or a hydroxyl group and uniformly disperses, thereby effectively acting on malodors (ammonia, hydrogen sulfide, trimethylamine, etc.) other than aldehyde compounds. Furthermore, in the present invention, if necessary, 0.02 to 2 parts by weight, preferably 0.1 to 1 part by weight, of a blocking inhibitor is used in combination with 100 parts by weight of the acetoacetyl group-containing polymer compound. You can also. Examples of such an antiblocking agent include inorganic and organic fine powders, for example, fine particles such as silicon dioxide, titanium dioxide, styrene, and methyl methacrylate.

The most important feature of the present invention is to laminate the above-mentioned thermoplastic resin film, particularly preferably a polyvinyl alcohol-based film, and an acetoacetyl group-containing polymer compound layer, and the laminating method is not particularly limited. For example, there is a method of coating a thermoplastic resin film with an acetoacetyl group-containing polymer compound, or a method of dry laminating an acetoacetyl group-containing polymer compound previously formed into a film or a sheet on a thermoplastic resin film. . When laminating, either one side or both sides of the thermoplastic resin film may be used. However, in the case of laminating on only one side, it is preferable that the base material such as a fiber product is disposed on the acetoacetyl group-containing polymer compound layer laminating side.

As a method of coating the acetoacetyl group-containing polymer compound on the thermoplastic resin film, water or dimethyl sulfoxide, dimethylformamide, dimethylacetamide, ethylene glycol, glycerin, diglycerin, hexa It is dissolved in an organic solvent such as fluoroisopropanol alone or as a mixture, and is appropriately performed by a known coating method such as a roll coater method, an air doctor method, a blade coater method, a spray method, and a dip method.
The coating amount in the coating was 0.1% in thickness after drying.
It is preferably from 30 to 30 μm, more preferably from 2 to 20 μm. If the thickness is less than 0.1 μm, the formaldehyde deodorizing ability and retention ability will be insufficient, and if it exceeds 30 μm, coating problems will occur and the surface condition of the film will deteriorate, which is not preferable.

As a method of dry laminating an acetoacetyl group-containing polymer compound previously formed into a film or a sheet on a thermoplastic resin film, a method of casting an acetoacetyl group-containing polymer compound from a solution,
5 to 1 by dry film forming method, gel film forming method, melt film forming method, etc.
A method of forming a sheet or film so as to have a thickness of 00 μm, preferably 10 to 50 μm, and laminating through a urethane-based, polyether-based, polyester-based adhesive or the like may be used.

The aldehyde-absorbing film of the present invention thus obtained is not particularly limited in its use, and the object (sheet, film,
Packaging, cover, rug, etc. for foam, woven fabric, knitted fabric, paper and fiber (woven fabric, non-woven fabric), wood (including those coated with adhesives and paints), etc. It is particularly useful for packaging of textiles and the like.

The aldehyde-absorbing film of the present invention comprises
It is extremely effective in reducing formaldehyde generated from an object containing formaldehyde or a base material, and does not cause formaldehyde migration or bleeding.

[0024]

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. As the acetoacetyl group-containing polyvinyl alcohol resin, the following (a-1)
To (a-3) were used. (A-1); acetoacetyl group-containing polyvinyl alcohol resin having an acetoacetyl group content of 10 mol%, a degree of polymerization of 1400, and a saponification degree of 89 mol% (a-2); acetoacetyl group content of 5 mol%, polymerization Acetoacetyl group-containing polyvinyl alcohol resin having a degree of hydrolysis of 1400 and a saponification degree of 94 mol% (a-3); acetoacetyl group content of 0.8 mol%, polymerization degree of 1400 and saponification degree of 98 mol% containing an acetoacetyl group Polyvinyl alcohol resin

Example 1 An aqueous solution (concentration: 22%) of a polyvinyl alcohol resin (degree of polymerization: 1700, degree of saponification: 99 mol%) was formed into a film by a casting method, and dried to obtain a polyvinyl alcohol-based film having a thickness of 30 μm. . The polyvinyl alcohol-based film is coated with an aqueous solution (concentration: 7%) of an acetoacetyl group-containing polyvinyl alcohol-based resin (a-1) using a gravure roll, and dried (thickness after drying is 10 μm) to absorb the aldehyde of the present invention. A film was obtained.
The following evaluation was performed about the obtained aldehyde absorption film.

(Aldehyde absorption power)
A bag having a size of 250 mm × 250 mm was prepared, and 2.5 g of formalin-treated cloth (free formalin amount: 600 ppm) was put in the bag and sealed by heat sealing. After that, 40 ° C x 65%
The sample was left standing under RH, sampled with time, and the amount of formalin remaining on the cloth was measured according to JIS L 1041 (acetylacetone method (method B)).

(Migration) 150 mm × 25 mm
A bag of 0 mm is made and a formalin-treated cloth 2.5
g (the amount of free formalin was 600 ppm) and sealed with heat sealing. A cloth that has not been subjected to formalin processing (free formalin content is 0 ppm) is brought into contact with the bag, and the bag is further wrapped in an aluminum bag.
H. After standing for 7 days, the amount of formalin transferred to a cloth that had not been subjected to formalin processing after 7 days was determined according to JIS L 1041.
(Acetylacetone method (Method B)). The evaluation criteria are as follows. ○: less than 10 ppm △: less than 10 to 200 ppm ×: 200 ppm or more

Example 2 The procedure of Example 1 was repeated, except that the acetoacetyl group-containing polyvinyl alcohol resin (a-1) was changed to the acetoacetyl group-containing polyvinyl alcohol resin (a-2). did.

Example 3 The procedure of Example 1 was repeated, except that the acetoacetyl group-containing polyvinyl alcohol-based resin (a-1) was changed to the acetoacetyl group-containing polyvinyl alcohol-based resin (a-3). did.

Example 4 An acetoacetyl group-containing polyvinyl alcohol resin (a
After preparing a film having a thickness of 20 μm from the aqueous solution (concentration: 20%) of -1) by a cast film forming method, the film is applied to the same polyvinyl alcohol-based film as in Example 1 via a urethane-based adhesive (adhesive Layer thickness 2 μm),
Lamination was performed to obtain the aldehyde-absorbing film of the present invention.

Example 5 The procedure of Example 1 was repeated except that the polyvinyl alcohol-based film was changed to a polypropylene film, and the same evaluation was performed.

Comparative Example 1 An evaluation was performed in the same manner as in Example 1 except that the polyvinyl alcohol-based film (a-1) containing no acetoacetyl group was used and only the polyvinyl alcohol-based film was used.

Comparative Example 2 An aldehyde deodorant composed of urea was applied to the same polyvinyl alcohol-based film as in Example 1 (thickness after drying was 10%).
μm) was evaluated in the same manner.

Comparative Example 3 One part of an aldehyde deodorant consisting of urea was added to 100 parts of a 10% aqueous solution of a polyvinyl alcohol resin (degree of polymerization: 1700, degree of saponification: 99 mol%), and the mixture was stirred. A film was prepared, and the film was evaluated in the same manner as in Example 1. Table 1 shows the results of Examples and Comparative Examples.
Shown in

[0035]

TABLE 1 aldehyde absorption migration resistance Initial 1 days after 7 days after 3 days Example 1 600 70 40 30 ○ 〃 2 600 80 70 50 ○ 〃 3 600 0.99 125 100 ○ 〃 4 600 50 30 20 ○ 〃 5 600 200 150 120 ○ Comparative example 1 600 400 350 300 × 〃 2 600 350 280 250 × 〃 3 600 300 250 200 △

[0036]

The aldehyde-absorbing film of the present invention is excellent in reducing formaldehyde generated from a base material because a acetoacetyl group-containing polymer compound layer is laminated on a thermoplastic resin film, particularly a polyvinyl alcohol-based film. It is effective in various uses such as packaging, covering, and rugs without formaldehyde migration and no bleeding.

Claims (5)

[Claims] 1. An aldehyde absorbing film comprising a thermoplastic resin film and an acetoacetyl group-containing polymer compound layer laminated on each other. 2. An aldehyde-absorbing film, wherein the thermoplastic resin film is a polyvinyl alcohol-based film. 3. The acetoacetyl group-containing polymer compound,
3. The aldehyde-absorbing film according to claim 1, which is an acetoacetyl group-containing polyvinyl alcohol-based resin. 4. The aldehyde absorption film according to claim 1, wherein the acetoacetyl group-containing polymer compound layer is laminated by coating. 5. The aldehyde-absorbing film according to claim 1, wherein the acetoacetyl group-containing polymer compound layer is laminated by dry lamination.