JPS5855977B2 - Gooseijiyuushiseihinnoshiyorihouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating synthetic resin products for preventing plasticizer migration in synthetic resin products using plasticizers and/or for preventing dye transfer in synthetic resin products colored with dyes or high-grade pigments. .

More specifically, by forming a specific synthetic resin coating on the surface of a colored synthetic resin product, it has excellent water resistance and solvent resistance, as well as excellent ability to prevent plasticizer migration and/or dye transfer. The present invention relates to a method for treating synthetic resin products that can be coated.

Conventionally, sheets made of synthetic resins such as soft vinyl chloride resin, urethane resin, and nylon, sheets lined with paper, textiles, stockinette, etc., and polyamide resins, polyurethane resins, etc. on the surface of products such as leather, leather, and textiles have been used. Apply,
Products that are dyed in a warm bath or coated on the surface of the product with a solution of the resin and organic solvent containing soluble dyes or pigments are often used because of their clear colors and transparency.

However, when synthetic resin products obtained in this way are sewn or transported as products, if they come into contact with other white or light-colored products, the dyes or pigments in the synthetic resin products will migrate, resulting in transfer of color to other products. and are often the subject of complaints.

In addition, in the field of synthetic leather, there is a demand for the development of soft-touch leather, and leather softened with plasticizers has been applied as a way to satisfy such demands; Because the plasticizer in the leather that has been used in the leather often has a lower molecular weight than the leather substrate, the plasticizer often migrates easily, and the performance of the leather changes over time due to the plasticizer migration, an undesirable phenomenon. It is known that various types of

For example, in the case of vinyl chloride leather, which has traditionally been used as car seats, the car is shipped by ship for export.
A simple example of this is when leather is impregnated with plasticizers that evaporate and adhere to various parts of the interior of a car as it passes through tropical regions at low latitudes.

Moreover, in the case of leather using plasticizers, dye transfer is likely to occur along with migration of the plasticizer, and there has been a strong desire for a method to prevent these phenomena.

Several methods have already been disclosed for preventing dye transfer of synthetic resin products, such as leather.

That is, JP-A-49-30502 discloses that dye transfer resistance is imparted to synthetic leather by applying a copolymer solution consisting of alkyl methacrylate and another ethylenically unsaturated monomer having a carboxyl group to synthetic leather. That is stated.

However, the coating formed by this method has poor solvent resistance, as when an amino acid resin dissolved in a solvent is applied thereon, it dissolves in the solvent, weakening the dye transfer effect, and in addition, the copolymer Coalescence has the disadvantage of extremely poor dye transfer resistance in wet conditions, probably because it has a large number of carboxyl groups in its molecules.

In view of these circumstances, the present inventors have completed the method of the present invention as a result of intensive research in order to solve the above-mentioned drawbacks.

An object of the present invention is to treat synthetic resin products with a coating composition that has excellent solvent resistance and excellent ability to prevent plasticizer migration and dye transfer, particularly in wet conditions.

That is, the present invention applies a coating of 20 to 80% on the surface of a synthetic resin product.
A copolymer consisting of an ethylenically unsaturated monomer having a carboxyl group and an acrylic acid ester and/or a methacrylic acid ester in weight percent, a blocked isocyanate compound, a polyN alkoxymethyl melamine compound, a polyepoxy compound, a polyoxazoline compound, At least one crosslinking agent selected from a polydihydroxazine compound, a low molecular weight polyol compound, and a polyamine compound is combined with a carboxyl group in the crosslinking agent and a crosslinkable functional group per equivalent of carboxyl group in the copolymer. A mixture of 0.01 to 0.7 equivalents is coated and then heat cured to provide solvent resistance, plasticizer migration resistance and/or dye transfer resistance. This is a method for processing synthetic resin products.

The method of the present invention will be explained in more detail below.

The synthetic resin products to be coated in the method of the present invention include leather made of vinyl chloride resin, urethane resin, amide resin, acrylic resin, styrene resin, acrylonitrile resin, polyester, polyolefin, etc., and colored with dyes, pigments, etc. , synthetic resin products such as leather, sheets, wallpaper, and fibers, molded products whose surfaces are treated with a surface treatment agent such as urethane resin, nylon, and amino acid resin, or paper, wood, and the like can be used.

In the present invention, the ethylenically unsaturated monomer having a carboxyl group, which is a member of the coating composition used for treating synthetic resin products, is not particularly limited as long as it is a known one, but for example, acrylic acid , methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic acid half ester, and crotonic acid.

These form copolymers with other members of the coating composition of the present invention, acrylic esters and/or methacrylic esters, and with further constituents, blocked incyanate compounds, polyN-alkoxy In combination with crosslinking agents such as methylmelamine compounds, polyepoxy compounds, polyoxazoline compounds, polydihydroxazine compounds, polyol compounds, and polyamines, they not only effectively prevent plasticizer migration and dye transfer, but also produce synthetic resin products. It has the effect of adhering to the surface when applied to the surface.

Other acrylic esters and methacrylic esters constituting the coating composition used in the present invention are not particularly limited, but include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, and isopropyl acrylate. , n-propyl acrylate, n-acrylate
-butyl, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, chloromethyl acrylate, chloroethyl acrylate, 2-acrylate
Hydroxyethyl, ethylene diacrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-methacrylate
Butyl, n-hexyl methacrylate, n-methacrylate
-octyl, chloromethyl methacrylate, chloroethyl methacrylate, glycidyl methacrylate, and the like.

The copolymer of an ethylenically unsaturated monomer having a carboxyl group and an acrylic ester and/or a methacrylic ester, which is a member constituting the coating composition used in the present invention, is an ethylenically unsaturated monomer having a carboxyl group. It is preferable to use a copolymer containing 20 to 80% by weight of copolymer.

If the proportion of the ethylenically unsaturated monomer having a carboxyl group in the copolymer is less than 20% by weight, the effect of preventing plasticizer migration and dye transfer will not be obtained substantially;
If this occurs, the solvent resistance of the coated product and the dye transfer resistance when wet are deteriorated, which is undesirable.

In addition, in the present invention, the above copolymer may optionally contain acrylic ester, methacrylic ester, and ethylenically unsaturated monomer having a carboxyl group in an amount of 20 mol% or less of the monomers constituting the copolymer. Other monomers copolymerizable with the monomer can also be used as copolymer components.

Examples of such monomers include acrylamide, methylolated acrylamide, methacrylamide, methylolated methacrylamide, acrylonitrile, methacrylonitrile, styrene, vinyl chloride, vinyl acetate, butadiene, isoprene, and the like.

The copolymer used in the present invention can be easily synthesized by known methods.

That is, methods include radical polymerization using a certain type of initiator, ionic polymerization, light, heat, radiation, and the like.

Further, depending on the monomers used and the polymerization method, the polymerization form can be a lump, a solution, a suspension, an emulsion, or a combination thereof.

However, depending on the type of initiator and monomer, for example, if the initiator reacts or decomposes with water, other polymerization methods must be used.

A particularly preferred polymerization method for obtaining the copolymer used in the present invention is a method using a radical generating catalyst.

For example, peroxides, oxygen, azo compounds, heat, light, radiation, organometallic compounds, etc. can be used arbitrarily.

Appropriate redox catalysts are also commonly used.

There is no particular restriction on the molecular weight of the copolymer used in the present invention, but the intrinsic viscosity is 0.02 to 10 dll? , preferably 0.1 to 2 dllf? The thing is (used).

Further, the other member constituting the coating composition for treating the synthetic resin product of the present invention is a blocked incyanate compound, a polyN-alkoxy-methylmelamine compound, a polyepoxy compound, a polyoxazoline compound, a polydihydroxazine compound. , at least one crosslinking agent selected from polyol compounds and polyamine compounds, more specifically toluene diisocyanate blocked with phenol, caprolactam, malonic acid diester, hydrogen cyanide, diphenylamine, succinimide, acetoacetate, etc. Blocked isocyanate compounds such as incyanate compounds such as diisocyanate diphenylmethane and prepolymers obtained with them and polyols and polyamines, hexamethylolmelamine hexamethyl ether, pentamethylolmelamine trinotyl ether, tetramethylolmelamine tetramethyl ether, trimethylolmelamine dimethyl ether, hexamethylol melamine hexaethyl ether,
Polyepoxy compounds such as poly N-alkoxymethyl melamine compounds such as hexamethylol melamine hexabutyl ether, bisphenol A diglycidyl ether, diglycidyl ether, butadiene dioxide, and epoxy prepolymers which are reactants of these and various polyols; Hexamethylene diamine, tetramethylene diamine, ethylene diamine, diaminodiphenylmethane,
Polyamine compounds such as diaminodiphenylpropane and phenylenediamine, polyol compounds such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dihydroxydiphenylpropane, dihydroxydiphenylmethane, and glycerin, 2,2'-tetramethylene (4・4-dimethyl-2-oxazoline), 22'-hexamethylene (4,4-dimethyl-2-oxazoline)
, oxazoline compounds such as 2,2'-phenylene (4,4-dimethyl-2-oxazoline), 5,6-sihydro 4H-1,3-oxazine, ■,3- and 1,4-
Bis(5',6'-dihydro-4'H-1',3'-oxazin-2'-yl)benzene, 1,3 and 1,4
-bis(5',5'-dimethyl-5',6'-dihydro-4'H-1',3'-oxazin-27-yl)-benzene, ■,3 and 1,4-bis-(6 '-methyl-
Examples include polydihydroxazine compounds such as 5', 5'-dihydro (4'H-1', 3'-oxazin-2'-yl)-benzene, and among these compounds, epoxy compounds in particular cause remarkable transfer, It is preferable because it exhibits the effect of preventing plasticizer migration.

Further, polyamine compounds and polyol compounds may be used in combination with dehydrating agents such as dicyclohexylcarbodiimide, triphenylphosphite, diphenylphosphite, diphenyl sulfide, and the like.

In the present invention, the above compound is applied as a crosslinking agent that undergoes a crosslinking reaction with the carboxyl group in the copolymer and imparts solvent resistance, dye transfer resistance, plasticizer migration resistance, etc. The ratio of the crosslinking agent used in the copolymer is 0.001 to 1 equivalent, preferably 0.001 to 1 equivalent of a functional group capable of crosslinking with a carboxyl group in the crosslinking agent per equivalent of carboxyl group in the copolymer. The amount ranges from 0.01 to 0.7 equivalents.

If the amount of the functional group capable of crosslinking with the carboxyl group is less than 0.001 equivalent per equivalent of the carboxyl group in the copolymer, the dye transfer prevention effect in a wet state will be significantly reduced.
On the other hand, if the amount exceeds 1 equivalent, the coating film becomes hard, making it unsuitable for certain uses, and the effect of preventing dye transfer is also reduced, which is not preferable.

In carrying out the present invention, any method can be used to coat the synthetic resin product with the coating composition, but a method in which the coating composition is applied in a state in which it is dissolved in a solvent is particularly preferred.

As the solvent for the copolymer, aromatic hydrocarbons, halogenated hydrocarbons, ketones, ethers, esters, amides, etc. are preferably used.

More specific examples include benzene, toluene, xylene, perchloroethylene, acetone, methyl ethyl ketone ethyl acetate, tetrahydrofuran, 1.4 dioxane, cyclohexanone, N-N-dimethylformamide and the like.

There is no particular restriction on the concentration of the processing agent solution, but for example, 1 to 50
A treatment agent solution of 5% to 30% by weight is used, preferably 5% to 30% by weight.

The viscosity of the processing agent solution is preferably 1 to 10.0000 centipoise, particularly 10 to 100 centipoise.

The coating composition prepared as described above can be applied to the surface of a synthetic resin product using various methods such as a doctor knife coater, a roll coater, a gravure printer, spraying, dipping, and brush coating, depending on the shape of the substrate to be coated. On the other hand, the solid content per square meter is 0.01 to 200 t,
Preferably, after applying it to 1 to 1001, 30
Heating at ~200°C causes crosslinking reaction.

Coloring agents for synthetic resin products that can prevent dye transfer by the method of the present invention include dyes and organic pigments in general.

Specific examples of the dye include, but are not limited to, direct dyes, acid dyes, alloy dyes, cationic dyes, oil-soluble dyes, reactive dyes, and disperse dyes.

In particular, metal-containing dyes, acid dyes, oil-soluble dyes, and the like are preferably used.

In addition, as plasticizers for synthetic resin products that can prevent the migration of plasticizers, phethalic acid diesters, resin group dibasic diesters, phosphoric acid triesters, glycol esters, etc. are used, specifically dibutyl phthalate. , dioctyl phthalate, dilauryl phthalate, butyl lauryl phthalate, butylbenzyl phthalate, dioctyl adipate, dioctyl sebacate, tricresyl phosphate, glycerin monostearate, etc., but are not limited thereto.

In addition, in the method for treating synthetic resin products using the coating composition of the present invention, the coating composition itself that is applied to the present invention has dye receptivity and also shares dye transfer resistance and plasticizer migration resistance. Therefore, dyes, pigments, etc. may be dispersed and mixed when the coating composition is dissolved in an organic solvent solution before coating.

Furthermore, ultraviolet absorbers, antioxidants, antistatic agents, etc. can be added as necessary.

The upper surface of the synthetic resin product treated in this manner can be further coated with a known surface treatment agent such as acrylic resin, urethane resin, or amino acid resin.

As described above, the method of treating the surface of synthetic resin products with a coating composition according to the method of the present invention imparts excellent transfer resistance, plasticizer migration resistance, and solvent resistance to synthetic resin products, and improves synthetic leather. For example, it has the remarkable advantage of having performance very similar to natural leather.

Further, since the coating composition used in the treatment of the present invention uses a specific crosslinking agent, it has the advantage of having a long pot life and being easy to handle.

The method of the present invention will be explained in more detail with reference to Examples below, but the method of the present invention is not limited thereto.

Example 1 A reflux condenser and a thermometer were attached to a 500 mA' Separate Flush flask, and the system was thoroughly purged with nitrogen. Then, 60 oz of butyl acrylate was added to 20 oz of methyl ethyl ketone as a solvent.
P, 4 liters of acrylic acid were charged, 1 liter of azobisisobutyronitrile was added after polymerization had been completed, and the polymerization was carried out at 70°C for 3 hours.
A solution of S' in methyl ethyl ketone of 31' was added, and the mixture was further polymerized at 70°C for 3 hours and then at 80°C for 1 hour.

10 g of this copolymer solution was colored with 0.5 y' of bisphenol A diglycidyl ether with methyl ethyl kesminol Mirinda Black B (dye manufactured by Sumitomo Chemical Co., Ltd., registered trademark), and the above treatment solution was applied to polyurethane leather. Coat with a bar coater to a thickness of 38μ, dry at room temperature for 3 hours,
A crosslinking reaction was carried out at 0°C for 20 minutes.

Next, a colored leather obtained by subjecting white vinyl chloride leather containing 60 parts by weight of dioctyl phthalate as a plasticizer to 100 parts by weight of vinyl chloride resin to 6Crt
' L x 6 Crr L, sandwiched the top and bottom between glass plates to shade the load of 3 kg, and left to dry at 80°C for 2 hours, contaminating the density of the color transferred from the colored urethane leather to the white vinyl chloride leather. gray scale (JIS
L-0805-1974).

The evaluation ranges from 1st grade to 5th grade, and the higher the number, the less dye transfer occurred, and in this case, it was grade 5.

Incidentally, the dye transfer in the untreated case, which was carried out for comparison, was grade 1.

Furthermore, the colored leather and white vinyl chloride leather treated above were each cut into 6 cm x 6 CTL pieces, soaked in ion-exchanged water for 10 minutes, and then the surfaces were overlapped, sandwiched between glass plates in the same manner as above, and a load of 3 kg was applied to a height. After being left at 80°C for 2 hours in a humid state, dye transfer in the humid state was examined.

In this case, it was grade 5-4.

In addition, as a result of conducting the same dye transfer test as above on the same colored urethane leather coated with only the above copolymer solution without adding the above crosslinking agent and dried, it was found that when dried, it was grade 5,
It was grade 2 when wet.

Further, the above treatment agent solution was applied to a thickness of 0.17712 m on a glass plate, dried at room temperature for 3 hours in the same manner as when treating leather, and then subjected to a crosslinking reaction at 120° C. for 20 minutes.

The membrane thus produced was made of methyl ethyl ketone, N-
It was insoluble in solvents such as N-dimethylformamide.

Next, 2mrrJ' containing 50 parts by weight of dioctyl phthalate as a plasticizer per 100 parts by weight of vinyl chloride resin.
Punch out a J-vinyl chloride sheet with a diameter of 50 mm and cut it at 70°.
After drying for C1 hour, the above treatment agent was applied to both surfaces to a thickness of 50 μm and dried.

After a further crosslinking reaction at 120°C for 20 minutes, the sample was sandwiched between top and bottom polystyrene plates and 7 kg was applied under a load of 2 kg.
The sample was left for 24 hours at 0° C. and 90% humidity, and the change in weight was measured.

As a result, the amount of plasticizer transferred to the polystyrene plate was 158 m9/ctI1 when the above treatment agent was not applied. On the other hand, when the above treatment agent is applied, it is 0.42 m9/ca.
decreased to

Based on the above results, the method of the present invention was used.

Synthetic resin products have excellent solvent resistance and plasticizer migration resistance.
It can also be seen that it has excellent dye transfer resistance in both wet and dry conditions.

Example 2 The monomers and crosslinking agents shown in Table 1 were used in the proportions shown in Table 1, and PVC leather was coated with Sumitop PC (registered trademark of Sumitomo Chemical Co., Ltd., a dyeing aid) and Spiron. The test was carried out in exactly the same manner as in Example 1 except that the dye was colored with Black BH Special (a dye registered by Hodogaya Chemical Co., Ltd.), and the results were as shown in Table 1.

Example 3 Spiron Black BH Special (registered trademark name of Hodogaya Chemical Co., Ltd., dye) 0.8'if was added to the coating composition prepared in Experiment No. 3 of Example 2 and mixed uniformly, and then coated on urethane leather. Coated.

This was examined for dye transfer resistance in the same manner as in Example 1, and was found to be grade 4 when dry and grade 3 when wet.

For comparison, a similar test was conducted on urethane leather colored using the same dye as in Example 3 at bath temperature, and the result was first grade both at dry and wet temperatures.

Claims (1)

[Claims] 1. On the surface of a synthetic resin product, a copolymer consisting of an ethylenically unsaturated monomer having 20 to 80% by weight of a carboxyl group and an acrylic ester and/or a methacrylic ester, a blocked incyanate compound, and a polyN - At least one crosslinking agent selected from an alkoxymethylmelamine compound, a polyepoxy compound, a polyoxazoline compound, a polydihydroxazine compound, a low molecular weight polyol compound, and a polyamine compound, per equivalent of carboxyl group in the copolymer. The ratio of carboxyl groups and crosslinkable functional groups in the crosslinking agent is 0.01
A method for treating a synthetic resin product, which comprises coating a mixture in an amount ratio of ~0.7 equivalent, and then crosslinking by heating.