JPS5936132A - Novel surface-treating agent - Google Patents

Abstract

PURPOSE:To obtain a novel surface-treating agent with high liquid stability, by carrying out a polymerization, in a nonhalogenated solvent, between a terminal amino group-contg. polyurethane resin and L-glutamic acid gamma-methyl ester N- carboxylic acid anhydride. CONSTITUTION:(A)100pts.wt. of a terminal amino group-contg. polyurethan resin and (B) 7-85pts.wt. of a L-glutamic acid gamma-methyl ester N-carboxylic acid anhydride are agitated for 3-5hrs. in combination with, if required, a tertiary amine as the catalyst, being heated to 50-70 deg.C followed by further agitation for 1-2hrs to carry out a polymerization, thus obtaining the objective surface-freating agent with a content of the polyamino acid portion of, pref. 5-40wt% of the whole resin. USE:For leather, matte finish, coloring, and for application as a resin for synthetic leather base.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyamino acid surface treatment agent with excellent liquid stability, and more specifically, a non-halogenated solvent such as dimethylformamide or dioxane for polyamino acid resin having an amine group at the end. L-glutamic acid r-methyl ester N-carbo/acid anhydride (
L-GNCA) (hereinafter abbreviated as L-GNCA) and, optionally, a tertiary amine catalyst, are copolymerized to provide a resin solution with excellent liquid stability as a surface treatment agent. be.

Conventionally, polyamino acid-based surface treatment agents have been used in large quantities as surface treatment agents or base resins in the production of artificial leather, synthetic leather, polyvinyl chloride leather, and natural leather. This is because when a resin is used for the surface treatment of fake leather, it can give an appearance and feel similar to natural leather, and also have excellent heat resistance and weather resistance. However, in conventional polyamino acid-based surface treatment agents, the solvent used is mainly composed of halides such as ethylene dichloride, methylene chloride, and trichloroethane.

However, halogenated solvents not only have a unique odor but are also considered undesirable in terms of health management of workers due to contamination of the working environment. Use is limited υ
There is one.

Therefore, due to the excellent properties of amino acid-based surface treating agents, there is a strong demand for the development of so-called non-halogenated solvent type amino acid-based surface treating agents that do not use halogenated solvents.

Conventionally, polyamino acids have a helical structure even in solvents, and it has been believed that they cannot maintain solubility unless a halogenated solvent is used as a helical solvent.

For example, if another solvent is used as a diluent, although it initially exhibits good fluidity, it may thicken over time and solidify into an agar-like state.

There are also known methods for producing modified polyamino acid solutions that have been studied in the past that do not use the halogenated layer J\11, but it has been confirmed that all of these methods solidify into an agar-like state during long-term storage.

This invention was discovered as a result of research on the Sharpness 1jJf Bui- for the purpose of improving the liquid stability of a solution of a modified polyamino acid group in a non-halogenated solvent as a surface treatment agent.

That is, this invention uses dimethyl fosolemamide (DM
F) Add L-GNCA to dioxane (DOX) solution,
A polyamino acid chain is added using a terminal amine group as a starting species, and a tertiary amine is used as an IJ, rA synthesis catalyst if necessary.

In order to obtain a stable copolymer resin solution in this invention, it is preferable that the content of the polyamino acid moiety is 40% by weight or less in the total resin content. However, a stable resin solution will not be obtained unless a logenated solvent is used in combination.

On the other hand, if the content of the polyamino acid moiety is less than 5, the stability of the resin solution is excellent, but the characteristics of the polyamino acid as a surface treatment agent are lost, which is not preferable.

Next, the solvent used in this invention is DMF.

DOX is preferable, and in addition, four agents such as methyl ethyl ketone (MEK), toluene (TOL), inpropatol (IPA), and 7'metallic acid ('MEOH) are used without impairing the stability of the solution. It is possible to use it as a diluted All in the range.

Incidentally, it is necessary to use the above-mentioned DMF or DOX in at least 60% of the total solvent.

The method for producing the polyurethane resin having terminal amine groups used in this invention is as follows.

Depending on the type of eel, a low-molecular vertical diol is added to polyester diol or polyether diol alone or in a mixture, and an organic diisocyanate is added to this to obtain a prepolymer having incyanate groups at the terminals.

Next, the above prepolymer is gradually added to a diamine solution prepared separately, and then an instant extension is performed.

At the end point of the reaction, the terminal amine group is determined, and the terminal amine group is regarded as -NH2 group, and the weight ratio is 500 to 3000.
Set two points in PPM's Aia box.

Next, to produce a polyamino acid-based polyurethane resin copolymer, a solution containing 100 parts by weight of a polyurethane resin having terminal amino groups is added with L-GNCA 7 to 85 stitches and optionally a tertiary amine catalyst for 0 days. Stir for 3-5 hours,
Next, the temperature was raised to 50-70°C and the mixture was stirred for 1-2 hours.

(The solution given as above may be made to have a higher viscosity by further adding isoneanate.The amount of terminal amino groups of the polyurethane resin used in this reaction is determined by the amount of L
- It is necessary to determine the amount appropriately depending on the amount of GNCA. When L-GNCA is used [L-GNCA is small, it is preferable to use a polyurethane resin with a high polyurethane weight.

Conversely, when a large amount of L-GNCA is used, it is preferable to use a polyurethane resin with a large amount of terminal amino groups and a relatively low molecular weight.

When using a polyurethane resin with a relatively high molecular weight and a small amount of terminal amine groups, and increasing the usage ratio of L-GNCA,
Products often lack stability.

The use of catalysts has the effect of improving solution stability.

For example, if a copolymerization reaction is carried out without using a catalyst, the stability of the solution may be somewhat lacking. In such cases, the use of catalysts improves stability. Although the details of this are not clear, it is likely that the reaction is accelerated due to a slight decrease in the viscosity of the solution, and the distribution width of the molecular weight of the polyamino acid moiety becomes smaller.

The modified polyamino acid resin solution obtained in this way may be further diluted as necessary to make a transparent processing agent, and optionally, a matting agent or pigment may be dispersed therein to produce a matting processing agent or a coloring processing agent. be.

This surface treatment agent only uses the same solvents used in conventional surface treatment agents and does not contain halogenated solvents, so there are no complaints about odor and it is extremely stable. It has been recognized that it has excellent properties not only as a surface treatment agent for fake leather, natural leather, and cloth, but also as a base for synthetic leather (as a lubricant).

The present invention will be explained in detail below with reference to Examples.

The number of copies is all for the upper and lower armpits.

Example (5) Production of polyurethane 1ηJ jiff 200 parts of polyethylene adipate having an average molecular weight of 1000, 3 parts of ethylene glycol, 131 parts of 4,4''-dicyclohegycylmethane diisocyaner) and 84 parts of doluol were charged into a polymerization vessel. , 4 to 105-110°C with stirring.
The prepolymer with terminal isocyanate groups is 14) kept for a period of time.

While stirring a separately prepared solution consisting of 40 parts of isophoronediamine and 884 parts of dimethylformamide, the prepolymer prepared above was added little by little at room temperature, and the terminal amino groups were measured. The reaction was stopped by stopping the addition of the prepolymer.

The polyurethane resin solution thus obtained had a concentration of 25% and a viscosity of 430 cps/at 30°C.

150 parts of dimethylformamide, 200 parts of dioxane, 150 parts of doluol, and 1 part of a 10-thidioxane solution of tributylamine were added to 240 parts of the 25% polyurethane resin bath solution obtained in the process for producing modified polyamino acid resin, and the mixture was stirred. L-GN at 25℃
50 parts of CA was added and held for 3 hours.

The temperature was then raised to 60°C, and after stirring for 1 hour, 70 parts of isopropanol, 100 parts of dimethylformamide, and 30 parts of doluol were added to obtain a modified polyamino acid) η (fat bath liquid) having a concentration of 10%.

The viscosity of this solution was l 25 cps/at 30°C.

The solution thus obtained is stored in a storage container at room temperature (approximately 25
The solution had good stability, with no increase in viscosity observed even after storage for one month at 40°C.

C) Preparation of surface treatment agent Add 4 parts of finely powdered silica (manufactured by Degussa, Erosil TT-600) and 8 parts of Dorol to 100 parts of the modified polyamino acid resin solution in (B), and disperse them uniformly to make them matte. Get a processing agent.

This treatment agent was coated on nylon taffeta with a knife at a concentration of 20 g/rIf, and then dried.

The resulting product had a texture similar to linen, and did not exhibit any slimy feeling characteristic of synthetic fibers.

It also had excellent dry cleaning resistance.

Example 2 (5) Manufacture of polyurethane resin As in (4) of Example 1, 600 parts of polybutylene adipate with an average molecular weight of 11,000, 36 parts of 44-butanediol, 444 parts of isophorone diisocyanate and 270 parts of doluol were mixed. A prepolymer was obtained in the same manner.

Separately, 1,620 parts of dimethylformamide was stirred in a container, and 46 parts of Pivezine was added and dissolved.To this solution, the above prepolymer was added little by little while stirring, and Terminal Amino Group Co., Ltd., 1984 PPM, 30°C. with a viscosity of 850
A urethane prepolymer with a concentration of 25% of cps was obtained.

(B) Production of modified polyamino acid resin 320 parts of polyurethane resin solution, 150 parts of dimethylformamide, 100 parts of dioxane, and 1 part of doluol
00 parts were placed in a polymerization container, and the L-
Add 26 parts of GNCA and stir for an additional 3 hours, then add 6 parts of GNCA.
After raising the temperature to 0° C. and stirring for 1 hour, 100 parts of doluol and isopropanol were added to bring the total amount to 800 parts.

The resulting solution had a concentration of 12.5 s and a viscosity of 800 cps.
/ at 30°C.

When this was stored at room temperature (approximately 25°C) for one month, the viscosity increased to 1200 cps, but did not increase after that.

Preparation of surface treatment agent 25 parts of doluol and 25 parts of inpropanol were added to 100 parts of the modified polyamino acid resin solution of ω) to prepare a surface treatment agent.

This treatment agent was applied to the surface of polyurethane synthetic leather for clothing using a gravure printer.

The surface of the obtained synthetic leather was dry and no stickiness was observed, making it an excellent synthetic leather for clothing.

Example 3 Using exactly the same material as in (g) of Example 2, the concentration was 25%.
A polyurethane resin solution containing 980 PPM of terminal amine groups was obtained. While stirring 100 parts of this solution, L
Add 20 parts of a 20% solution of -G N CA in dioxane, then add 0.0 parts of a 10% solution of triethylamine in dioxane.
6 parts were added and stirred for 4 hours.

The solution thus obtained had a viscosity of 2800 cps at 30°C and excellent storage stability.

When 100 parts of this solution was sampled and isophorone diamine was added dropwise little by little while stirring at room temperature, the viscosity increased and
A solution of 8000 cps was obtained at '''C.

This was diluted with an equal volume mixed solvent of isopropanol, doluol, and methanol to obtain a solution of 4000 cps.

Using this polymer solution, synthetic leather was produced by a transfer method using release paper.

When this was used as a base material for shoes, it had an excellent feel and did not exhibit rubber-like elasticity.

As described above, this invention provides a surface treatment agent made of a modified polyamino acid resin that does not require any halogenated solvents, which has never been seen on the market. It is particularly excellent.

Patent applicant: Seiko Kasei Co., Ltd. Agent: Patent attorney Kazu1) Akira

Claims (1)

[Claims] A novel surface treatment with excellent liquid stability made by polymerizing a polyurethane resin with terminal amino groups and L-glutamic acid γ-methyl ester N-carboxylic acid anhydride in a solvent such as dimethylformamide or dioxane that does not contain a halogen solvent. agent.