JPH0819250B2 - Composition for preventing plasticizer migration - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition for preventing migration of a plasticizer, which is applied to a vinyl chloride resin containing a plasticizer.

[Conventional technology]

Recently, a soft vinyl chloride resin containing a large amount of a plasticizer has been widely used. However, the soft vinyl chloride resin is
By containing a large amount of plasticizer, various problems associated with the migration of plasticizer, such as blocking between films, contamination with printing ink on desk mats, application to soft vinyl chloride resin tape such as insulating tape It causes the deterioration of the pressure-sensitive adhesive, the peeling when used for laminating veneer hard boards, etc. These phenomena, for example, in desk mats, the plasticizer in the soft vinyl chloride resin migrates to the surface of the soft vinyl chloride resin,
It is caused by the plasticizer promoting contamination by the printing ink. In addition, for soft vinyl chloride resin tape,
The plasticizer transferred to the surface of the tape deteriorates the pressure-sensitive adhesive applied on the tape and accelerates peeling. Further, in the case of a soft vinyl chloride resin film for agriculture, it promotes blocking due to static electricity and adhesion of oils and dust to the film surface.

Therefore, in order to solve these problems, conventionally, a method of coating the surface of the soft vinyl chloride resin with a specific resin or paint has been proposed. For example, Japanese Patent Publication No. 61-29639 and Japanese Patent Publication No. 50-28117 propose a method of applying an acrylic acid resin to the surface of a soft vinyl chloride resin molded product. Further, JP-A-59-138239 discloses that
To a solution prepared by dissolving a copolymer of vinyl monomers having a functional group in a solvent, a polyisocyanate compound is added as a cross-linking agent, this solution is applied to a soft vinyl chloride resin leather, and the above copolymer is applied on the leather. A method of cross-linking is proposed. Furthermore, in JP-A-61-66726,
A method has been proposed in which a photopolymerizable oligomer is applied to a soft vinyl chloride resin film and the above oligomer is cured by irradiating light from a high pressure mercury lamp.

[Problems to be Solved by the Invention]

However, in the above-mentioned conventional method in which the surface of the soft vinyl chloride resin is coated with a specific resin or paint, the prevention performance for preventing migration of the plasticizer is insufficient. Further, the adhesion between the soft vinyl chloride resin and the above-mentioned resin or paint is poor, and improvement in this respect has been desired.

The present invention has been made in view of the above conventional problems, and an object thereof is to prevent migration of a plasticizer in a vinyl chloride resin and prevent plasticizer migration excellent in adhesiveness with the vinyl chloride resin. The present invention provides a composition for use.

[Means for solving the problem]

Methyl methacrylate used as a raw material in the production of the plasticizer migration preventing composition of the present invention is the above-mentioned methacrylic acid based on the total amount of the methyl methacrylate, the unsaturated monomer described below and other polymerizable unsaturated monomers. The amount of methylate is
It is used so that it is 61% by weight or more.

The unsaturated monomer used as a raw material in the production of the plasticizer migration preventing composition of the present invention, that is, an unsaturated monomer having a carboxyl group and copolymerizable with methyl methacrylate, for example, (Meth) acrylic acid, cinnamic acid,
Examples thereof include unsaturated monocarboxylic acids such as crotonic acid; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid; and monoesters of these carboxylic acids. Only one kind of these unsaturated monomers may be used, or two or more kinds thereof may be appropriately mixed and used.

In the production of the plasticizer migration preventing composition of the present invention, the other polymerizable unsaturated monomer used as a raw material, if necessary, is a monomer which can be copolymerized with the methyl methacrylate and the unsaturated monomer. The body is not particularly limited. As other polymerizable unsaturated monomers, for example,
(Meth) acrylamide, N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methyl acrylate, ethyl (meth) acrylate, n-
Propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylonitrile, styrene, α -Methylstyrene, vinyl acetate, vinyl propionate, (meth)
Examples thereof include acrolein, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like. Only one kind of these other polymerizable unsaturated monomers may be used, or two or more kinds thereof may be appropriately mixed and used.

The polymer that is a precursor for obtaining the composition for preventing migration of a plasticizer of the present invention is the above-mentioned methyl methacrylate, an unsaturated monomer, and, if necessary, other polymerizable unsaturated monomers. It can be produced by copolymerization using the above-mentioned polymerization method. As the polymerization method, for example, a solution polymerization method,
Bulk polymerization method, suspension polymerization method, etc. can be adopted,
In the present invention, it is most preferable to manufacture by the solution polymerization method. When the polymer is produced by a polymerization method other than the solution polymerization method, a step of dissolving the polymer in an organic solvent capable of dissolving the polymer is required.

When adopting the solution polymerization method, examples of the solvent that can be used include toluene, xylene, and other aromatic solvents such as aromatics having a high boiling point; ethyl acetate, butyl acetate,
Ester solvents such as cellosolve acetate; methyl alcohol, ethyl alcohol, isopropyl alcohol,
Examples thereof include alcohol solvents such as n-butyl alcohol and isobutyl alcohol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Only one kind of these solvents may be used, or two or more kinds thereof may be appropriately mixed and used.

Examples of the polymerization initiator that can be used in the above-mentioned polymerization method include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl-peroxide and the like. The reaction temperature is room temperature to 200 ° C, preferably 40 ° C
Within the range of ~ 120 ° C.

The composition for preventing plasticizer migration is obtained by reacting the carboxyl group of the above polymer with an alkyleneimine. That is, the composition for preventing plasticizer migration is obtained by aminating a polymer with an alkyleneimine.

Examples of the alkyleneimine used as a raw material in the production of the plasticizer migration preventing composition of the present invention include ethyleneimine, propyleneimine, butyleneimine, and the like. In addition, N- (2-aminoethyl) aziridine,
N- (aminoalkyl) alkyleneimines such as N- (3-aminopropyl) aziridine and N- (2-aminopropyl) propyleneimide can also be used in the same manner.

The amination reaction is, for example, 40 ° C to 150 ° C, preferably 5
It is achieved by mixing and stirring the above-mentioned polymer and alkyleneimine under a temperature condition within the range of 0 ° C to 100 ° C.

The compound obtained by the amination reaction is as it is,
The composition for preventing plasticizer migration of the vinyl chloride resin according to the present invention can be used, but the composition for preventing plasticizer migration is
If necessary, a diluent solvent may be appropriately contained.

[Action]

The composition for preventing migration of a plasticizer according to the present invention is a composition for preventing migration of a plasticizer applied to a vinyl chloride resin containing a plasticizer, which has methyl methacrylate and a carboxyl group, and has a methacrylic acid content. An unsaturated monomer copolymerizable with methyl and, if necessary, methyl methacrylate and another polymerizable unsaturated monomer copolymerizable with the unsaturated monomer are mixed with methyl methacrylate and an unsaturated monomer. The carboxyl group of the polymer obtained by copolymerization so that the amount of the methyl methacrylate is 61% by weight or more based on the total amount of the monomer and the other polymerizable unsaturated monomer, and reacted with alkyleneimine. It is a configuration.

This prevents the migration of the plasticizer in the vinyl chloride resin, imparts blocking resistance and stain resistance, and provides a composition for preventing plasticizer migration that has excellent adhesion to the vinyl chloride resin. You can

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, "part" described in Examples and Comparative Examples means "part by weight".

(Example 1) In a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube, 21 parts of isopropyl alcohol and 49 parts of toluene as solvents, 27.6 parts of methyl methacrylate, and unsaturated Methacrylic acid as a monomer 2.4
The department was prepared. Then, the reaction solution was heated to 80 ° C. while blowing nitrogen gas into the flask. The amount of methyl methacrylate is 92% by weight based on the total amount of methyl methacrylate and methacrylic acid. Further, no other polymerizable unsaturated monomer is used in the above reaction.

Next, while maintaining the reaction liquid at 80 ° C., 0.14 parts of azobisisobutyronitrile as a polymerization initiator was added over 7.5 hours in several batches. After the addition was completed, the reaction solution was further kept at 80 ° C. for 1 hour, and then the reaction solution was cooled to room temperature. As a result, a polymer solution having a carboxyl group was obtained.

Next, 1.3 parts of ethyleneimine as alkyleneimine was added dropwise to the reaction solution in the flask over 10 minutes. After 1 hour has passed since the end of the dropping, the reaction solution was heated to 75 ° C.
The temperature was raised to and maintained at the same temperature for 4 hours. Then, a distillation apparatus was set in the flask and heated under reduced pressure to distill off unreacted ethyleneimine together with isopropyl alcohol out of the reaction system. That is, unreacted ethyleneimine remaining in the reaction solution was completely removed. Then
Toluene as a diluting solvent was added to the reaction system to obtain a solution in which the non-volatile content was adjusted to 30% by the toluene, that is, a solution in which the plasticizer migration preventing composition was dissolved.

This solution was applied to both sides of a vinyl chloride resin film using a bar coater so that the film thickness would be 1 μm. Then, the vinyl chloride resin film was placed in a constant temperature bath kept at 120 ° C. for 2 minutes to dry the solution. The plasticizer migration-preventing composition applied to the vinyl chloride resin film as described above was subjected to various evaluations by the following evaluation methods. The results are shown in Table 1.

“Evaluation method” (1) Measurement of plasticizer migration amount A vinyl chloride resin film coated with a plasticizer migration preventing composition was cut into a circle having a diameter of 5 cm, which was then sandwiched between polyethylene sheets, which were then glass plates. Sandwiched between. In this state, a load of 5 kg was applied to the laminate, and the laminate was left in a constant temperature bath maintained at 70 ° C. for 24 hours. Then, the above laminate was taken out from the constant temperature bath, the load was removed, and the glass plate was removed. Then, the polyethylene sheet was peeled off from the vinyl chloride resin film, and the amount of the polyethylene sheet increased, that is, the amount of plasticizer transferred (mg) was determined. It is indicated that the smaller the value of the transfer amount of the plasticizer, the smaller the transfer amount of the plasticizer from the surface of the vinyl chloride resin film to the polyethylene sheet. Further, the state of the surface of the vinyl chloride resin film, that is, the state of the coating film surface of the composition for preventing plasticizer migration was observed.

(2) Stain resistance A vinyl chloride resin film coated with a plasticizer migration preventing composition is cut into a 5 cm × 5 cm square, and then adhered to a pre-exposed copy paper, which is then glassed. Sandwiched between plates. In this state, a load of 2 kg was applied to the laminate, and the laminate was left in a constant temperature bath maintained at 37 ° C. for 24 hours. Then, the above laminate was taken out from the constant temperature bath, the load was removed, and the glass plate was removed. Then, the vinyl chloride resin film was peeled off from the copy paper, and the stain resistance of the vinyl chloride resin film was observed. Also, after performing the same operation, 50
Contamination resistance was also observed for the vinyl chloride resin film left in a constant temperature bath kept at 0 ° C. for 24 hours.

The evaluation was made into the following three stages. That is, the state in which the vinyl chloride resin film was not contaminated by the carbon adhering to the exposed copy paper was indicated as ◯, the state in which a part was contaminated was indicated as Δ, and the state in which the whole was contaminated was indicated as x.

(3) Adhesion Adhesion was evaluated by using a so-called tape peel test using the vinyl chloride resin film used for measuring the amount of transferred plasticizer. The evaluation has the following two levels. That is, in the tape peeling test, the case where the coating film of the plasticizer migration preventing composition was not peeled from the vinyl chloride resin film was marked with ◯, and the case where it was peeled was marked with x.

(4) Creep test A vinyl chloride resin film coated with a plasticizer migration preventing composition was adhered to plywood with an adhesive, and after 1 day,
It was put in a constant temperature bath kept at 20 ° C. for 5 days for curing. Then, the vinyl chloride resin film was subjected to a creep test (tensile test). Also, after performing the same operation,
A creep test was also performed on the vinyl chloride resin film that had been aged for 5 days in a constant temperature bath maintained at 80 ° C. Then, according to the creep test, 180 degree peel strength (K
g / 25 mm) was measured. The measurement conditions were a measurement temperature of 20 ° C., a pulling speed of 200 mm / min, and a film width of 25 mm. In addition, Aroset NB-36 (trade name; manufactured by Nippon Shokubai Chemical Co., Ltd.) was used as an adhesive.

(Example 2) The amount of methyl methacrylate in Example 1 was set to 24 parts, further 3.6 parts of butyl methacrylate was used as another polymerizable unsaturated monomer, and the amount of ethyleneimine as alkyleneimine was 1.3 parts. Example 1 except that the above is used
The same reaction as in (1) was performed to obtain a solution in which the plasticizer migration preventing composition was dissolved. The amount of methyl methacrylate is 80% by weight based on the total amount of methyl methacrylate, methacrylic acid and butyl methacrylate.

Various evaluations were performed on this solution by the same evaluation method as in Example 1. The results are shown in Table 1.

(Example 3) The amount of methyl methacrylate in Example 1 was 18.3 parts, 9.3 parts of butyl acrylate was used as the other polymerizable unsaturated monomer, and the amount of ethyleneimine as the alkyleneimine was 1.3 parts. The same reaction as in Example 1 was carried out except that the above was used to obtain a solution in which the plasticizer migration preventing composition was dissolved. The amount of methyl methacrylate is 61% by weight based on the total amount of methyl methacrylate, methacrylic acid and butyl methacrylate.

Various evaluations were performed on this solution by the same evaluation method as in Example 1. The results are shown in Table 1.

Comparative Example 1 The same reaction as in Example 1 was carried out except that ethyleneimine was not used as the alkyleneimine in Example 1 to obtain a comparative solution in which the comparative plasticizer migration preventing composition was dissolved. .

Various evaluations were performed on this comparative solution by the same evaluation method as in Example 1. The results are shown in Table 1.

(Comparative Example 2) Various evaluations were performed by the same evaluation method as in Example 1 except that the composition for preventing plasticizer migration was not applied to the vinyl chloride resin film. That is, various evaluations were performed on the vinyl chloride resin film itself. The results are shown in Table 1.

[Effects of the Invention] The composition for preventing migration of a plasticizer of the present invention comprises methyl methacrylate, an unsaturated monomer having a carboxyl group, and copolymerizable with methyl methacrylate, and optionally methyl methacrylate. And other polymerizable unsaturated monomer copolymerizable with the unsaturated monomer, methyl methacrylate, the above-mentioned methyl methacrylate with respect to the total amount of the unsaturated monomer and other polymerizable unsaturated monomer Is obtained by reacting the carboxylic acid group of the polymer obtained by copolymerization so that the amount becomes 61% by weight or more with alkyleneimine.

This prevents migration of the plasticizer in the vinyl chloride resin, imparts blocking resistance, stain resistance, and reacts the carboxyl group of the polymer with the alkyleneimine. It is possible to provide a composition for preventing migration of a plasticizer having excellent adhesion. That is, by applying a plasticizer migration preventing composition to a vinyl chloride resin, various problems associated with the migration of the plasticizer, for example, blocking between films, contamination with printing ink on a desk mat, insulation, etc. It is possible to prevent the deterioration of the pressure-sensitive adhesive applied to a soft vinyl chloride resin tape such as a tape and the peeling when used for bonding a veneer hardboard or the like.

Claims (1)

[Claims] 1. A composition for preventing migration of a plasticizer which is applied to a vinyl chloride resin containing a plasticizer, wherein the unsaturated compound has methyl methacrylate and a carboxyl group and is copolymerizable with methyl methacrylate. The monomer and other polymerizable unsaturated monomer which can be copolymerized with methyl methacrylate and the unsaturated monomer as necessary are treated with methyl methacrylate, the unsaturated monomer and the other polymerizable unsaturated monomer. The amount of the above-mentioned methyl methacrylate is 61 with respect to the total amount of the saturated monomer.
A composition for preventing plasticizer migration, which comprises reacting a carboxyl group of a polymer obtained by copolymerization in an amount of not less than wt% with an alkyleneimine.