JPH0326041B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to artificial leather shoes, and more particularly to a method for efficiently manufacturing artificial leather shoes having a design on the surface.

b. Prior Art In recent years, artificial leather has been widely used as a shoe material instead of natural leather, and at the same time, a rational shoe molding method involves injecting molten resin into a shoe sole mold and simultaneously forming the sole. The so-called direct bottoming processing method (direct injection soleing), which performs bonding with an upper member made of artificial leather, has become popular. Synthetic rubber, unvulcanized rubber such as natural rubber, and polyvinyl chloride resin are used as the bottom resin, but blocks made of vinyl chloride resin and butadiene styrene are commonly used due to ease of processing and economic efficiency. Polymer resins have come to be mainly used.

However, since conventional artificial leather does not have sufficient adhesion to the bottom resin, it is necessary to apply a pre-treatment agent called a primer to the bottom surface of the artificial leather upper material and then injection mold the bottom resin. It was hot.

The primer contains a highly polar organic solvent and organic diisocyanate to increase adhesion, and if it adheres to surfaces other than the adhesive surface, it will cause disadvantages such as discoloration and deterioration of the artificial leather surface. It is necessary to carefully apply the molten resin to the areas to which it will adhere during injection molding, which requires manual labor, resulting in poor work efficiency and large costs, so there is a high demand for improvement.

c. Purpose of the Invention As a result of intensive study on a shoe processing method that enables soles to be attached by direct injection molding without using a primer, which causes such defects, the present inventors have developed an artificial leather upper material. We previously discovered and proposed a method of bonding shoes by direct sole attachment using artificial leather with a special polyurethane resin coating applied to the surface of the artificial leather base. However, with this method, when an attempt is made to apply a design by embossing the surface of the artificial leather with an embossing roll or the like with a design, the resin coating on the surface tends to block. There was a problem when I did this. In addition, if the heat resistance of the surface coating resin is improved to make it suitable for deep designs, the adhesion with the injected molten resin will not be sufficient.
If the design of the shoe is a cuff sole type, where the edge goes all the way to the top of the side of the shoe, the temperature drop at the edge will be large, and the shoe may peel off from the edge when actually worn. Sometimes it was hot.

The inventors of the present invention have conducted intensive studies to find a shoe that has a good balance between dry adhesive strength, which is required for practical adhesive strength, and wet adhesive strength, which is a problem when shoes are repeatedly washed with warm water. The present invention has been achieved by making it possible to provide artificial leather shoes with an excellent design using a rational processing method.

d.Structure of the Invention That is, the present invention involves fitting a shoe upper member made of artificial leather made of a fibrous base material and a rubber-like elastic body into a mold having a bottom mold that fits the upper member; In order to manufacture artificial leather shoes by injecting a molten resin mainly made of vinyl chloride resin to mold the sole and at the same time adhering it to the upper member, the artificial leather is made of a fibrous base material and a rubber-like elastic material. A film mainly composed of polyurethane resin [A] having a repeating unit represented by the following general formula [] and having a heat softening temperature of 130°C or higher is formed on the surface of an artificial leather base made of After applying pressure to give a design to the surface, a film mainly composed of polyurethane resin [B] having repeating units represented by the following general formula [] and having a heat softening temperature of 60 to 120°C is formed on the surface. This is a method for manufacturing artificial leather shoes, characterized by using artificial leather made from artificial leather.

[R ₁ is a divalent organic diisocyanate residue excluding the isocyanate group, R ₂ is a polymeric diol residue with a molecular weight of 800 or more excluding the hydrogen atom of the hydroxyl group, and R ₃ is a chain extender residue; A low molecular weight diol residue with a molecular weight of 200 or less excluding hydrogen atoms,
an aliphatic, alicyclic or aromatic diamine residue with one hydrogen atom removed from the amino group, or a hydrazine or hydrazine derivative residue with one hydrogen atom removed from the terminal amino group, l ₁ and m ₁ are 1 An integer greater than or equal to ] [R ₄ is an aliphatic or alicyclic organic diisocyanate residue, R ₅ is an aliphatic or alicyclic organic diisocyanate residue with a molecular weight of 1000 excluding the hydrogen atom of the hydroxyl group.
In the above polymeric diol residues, R ₆ is a chain extender residue, and is a low molecular weight diol residue with a molecular weight of 400 or less excluding the hydrogen atom of the hydroxyl group, or an aliphatic or aliphatic diol residue excluding one hydrogen atom of the amino group. Alicyclic diamine residue, l ₂ and m ₂ are integers of 1 or more. ] Artificial leather as used in the present invention refers to nonwoven fabrics, woven fabrics, knitted fabrics, or other fibrous base materials made of synthetic fibers, natural fibers, etc., to which a rubber-like elastic resin such as polyurethane elastomer or synthetic rubber is attached, or At least one surface is coated with a resin mainly composed of polyurethane elastomer so as to have a microporous structure, and this surface is coated with polyurethane resin, acrylic ester resin, cellulose resin, polyamide resin, polyurethane resin, etc. Refers to a coating made of amino acid resin or the like mixed with a coloring agent.

The method for producing the artificial leather substrate is not particularly limited, and can be performed by a conventionally known wet method, dry method, or the like.

The polyurethane resin [A] coated on the surface of the artificial leather of the present invention has a repeating unit represented by the above general formula [], and the organic diisocyanate used therein includes aliphatic, alicyclic, and aromatic diisocyanates. Specifically, aliphatic diisocyanates include tetramethylene diisocyanate,
linear organic diisocyanates such as hexamethylene diisocyanate and lysine diisocyanate;
Alicyclic diisocyanates include cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexyldimethylmethane-
4,4'-diisocyanate and the like. As the aromatic diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, etc. can be used.

In addition, the polymeric diol used for the polyurethane resin [A] has a hydroxyl group at both ends, a molecular weight of 800 or more, preferably 1000 to 3000, and a melting point of 70.
polyester glycols with melting points below °C;
These include polyether glycol, polyether ester glycol, polybutadiene glycol, etc. Typical examples are polyethylene adipate, polybutylene adipate, polycaprolactone glycol, polyoxyethylene glycol,
Polyoxypropylene glycol, polyoxytetramethylene glycol, etc. or mixtures thereof can be used. As a soft segment, those with a low degree of crystallinity and a low melting point have better adhesion, and in order to maintain adhesive durability in practical use, those with good hydrolysis resistance and microbial deterioration resistance are preferable, and diethylene adipate, propylene, adipate,
2,2-dimethyl-1,3-propanediol
10 to 40 mol% copolymerized butylene adipate,
2,2-dimethyl-1,3-propanediol
10 to 40 mol% copolymerized hexamethylene adipate, copolymer of adipic acid and polyethylene glycol, polypropylene glycol, polytetramethylene glycol alone or mixed diol with an average molecular weight of 150 to 600, polyethylene with an average molecular weight of 150 to 600 These include copolymers of glycol, polypropylene glycol, polytetramethylene glycol alone or mixed diols, and aliphatic dicarboxylic acids other than adipic acid.

Furthermore, as chain extenders, low molecular weight diols such as ethylene glycol, tetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and triethylene glycol, and aliphatic diols such as ethylene diamine, propylene diamine, and hexamethylene diamine are used. diamine, isophorone diamine, cyclohexylene diamine, 4,4'-diaminodicyclohexylmethane,
Alicyclic diamines such as 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, hydrazine such as methylhydrazine, phenylhydrazine, and benzylhydrazine, or dicarboxylic acids such as adipic acid and sebacic acid, and amino acids such as glycine and alanine. hydrazide, etc. can be used.

In order to achieve the object of the present invention, the heat softening temperature of the polyurethane resin [A] must be 130°C or higher. If the temperature is less than 130°C, blocking tends to occur during embossing for design, making it unsuitable. This thermal softening point temperature varies depending on the composition of the raw materials used for polymerizing the polyurethane resin, but the thermal softening point temperature is determined by the ratio of the number of moles of the chain extender to the number of moles of the polymeric diol (abbreviated as R'). It can be controlled by changing R′, and the thermal softening temperature increases.

In order to form a film of polyurethane resin [A] on an artificial leather substrate, a volatile organic solvent of polyurethane resin [A] is mixed, the viscosity is adjusted to 50 to 500 cps, and then gravure transfer method, reverse roll coating method, It can be applied by a Nycoat method, a spray method, etc., or by applying it to a release paper etc. and adhering it with or without drying. A coloring agent, a stabilizer, a gloss adjuster, etc. may be added to the organic solvent of the polyurethane resin [A]. The coating amount of the polyurethane resin [A] is usually 2 to 50 g/m ² in terms of solid content, preferably 5 to 20 g/m ² .

Next, an embossing roll or an embossing plate having a design is heated and pressed to transfer the design. In order to sufficiently incorporate the design into the artificial leather base coated with the polyurethane resin [A], the temperature, pressure, and pressing time during embossing may be adjusted, respectively.

The polyurethane resin [B] coated on the outermost surface of the artificial leather of the present invention has a repeating unit represented by the above general formula [], and the aliphatic diisocyanates used therein include tetramethylene diisocyanate, hexamethylene diisocyanate, and lysine. Linear organic diisocyanates such as diisocyanate, and alicyclic diisocyanates include cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexyldimethylmethane-4,4'-diisocyanate, and the like.

The reason why the above-mentioned diisocyanate is necessary for the polyurethane resin [B] is that the aromatic diisocyanate normally used in the production of polyurethane resin not only has poor yellowing resistance, but also has poor resistance to polyurethane elastomer consisting of an aromatic diisocyanate and a chain extender. This is because the crystal melting point of the hard segment becomes too high, and when it comes into contact with the heated and molten bottoming resin, there is insufficient softening activation due to heat, resulting in insufficient adhesive strength. It is necessary that sufficient softening activation by heat occurs and that there is no large difference in the crystallization rate between the molten resin used for bottoming and the cooling process, and for this purpose, aliphatic diisocyanates or It must be an alicyclic diisocyanate.

In addition, the polymeric diol used in the polyurethane resin [B] has hydroxyl groups at both ends, has a molecular weight of 1000 or more, preferably 1200 to 3000, and has a melting point.
These include polyester glycol, polyether glycol, polyether ester glycol, polybutane diene glycol, etc., which have a melting point of 70°C or less. Typical examples include polyethylene adipate, polybutylene adipate, polycaprolactone glycol, polyoxyethylene glycol, and Oxypropylene glycol, polyoxytetramethylene glycol, etc. or a mixture thereof can be used, but soft segments with a low degree of crystallinity and a low melting point have better adhesion and are important in maintaining adhesive durability in practical use. Those with good hydrolysis resistance and microbial deterioration resistance are preferred, such as diethylene adipate, propylene adipate, butylene adipate copolymerized with 10 to 40 mol% of 2,2-dimethyl-1,3-propanediol, 2,2- Hexamethylene adipate copolymerized with 10 to 40 mol% of dimethyl-1,3-propanediol, copolymerization of single or mixed diols of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol with an average molecular weight of 150 to 600 and adipic acid. copolymers of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, singly or mixed diols having an average molecular weight of 150 to 600, and aliphatic dicarboxylic acids other than adipic acid.

Further, the chain extender may be a low molecular weight diol such as ethylene glycol, tetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol or triethylene glycol, or a fat such as ethylene diamine, propylene diamine or hexamethylene diamine. alicyclic diamines such as isophorone diamine, cyclohexylene diamine, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, methylhydrazine, phenylhydrazine, benzylhydrazine, etc. or dicarboxylic acids such as adipic acid and sebacic acid, hydrazides of amino acids such as glycine and alanine, etc. can be used.

In order to satisfy the purpose of the present invention, the thermal softening point temperature of the polyurethane resin [B] needs to be 60 to 120°C, preferably 80 to 110°C. When the thermal softening point temperature exceeds 120° C., the thermal softening activation by the molten bottoming resin is insufficient, resulting in a lack of adhesion with the molten resin, which is undesirable. If the heat softening temperature is less than 60°C, it is not preferable because it will be heat softened by heat from a wiper etc. during shoe hanging, heat during the dry heat setting process, etc., and workability will be significantly impaired. In order to avoid this, it is preferable to use a method known as the California method, in which the insole and upper are double-stitched using a sewing machine.

The thermal softening temperature of polyurethane resin is determined mainly by the composition of the hard segment consisting of diisocyanate and chain extender, the proportion of the hard segment in the total resin, and the molecular chain length of the polyurethane resin. In order to achieve this, it is necessary to appropriately select the composition of the diisocyanate, the amount of hard segment, and the degree of polymerization of the resin. Generally, the softening temperature is increased by increasing the diisocyanate content and the amount of chain extender, and by increasing the degree of polymerization of the polyurethane resin. Regarding the composition of diisocyanates, those with high crystallinity and high molecular chain rigidity have a higher softening point, and chain extenders that have high crystallinity, high molecular chain rigidity, and low hydrogen bond density The larger the item, the higher it will be.

The method for producing the polyurethane resin [B] is not limited, but the polymer diol and diisocyanate are prepared so that the value of [number of moles of diisocyanate]/[number of moles of polymer diol] is 2 or more, and the method is prepared in a solvent-free manner or with respect to isocyanate. A preferred method is to react in a non-reactive organic solvent to prepare a prepolymer having isocyanate groups at the terminals, and then add a chain extender to carry out a chain extension reaction. The chain extension reaction can be carried out in a single or mixed solvent such as dimethylformamide, dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide, diethylformamide, dioxane, and tetrahydrofuran. In order to make a paint for painting from the obtained polymer, an appropriate amount of a low boiling point solvent such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl acetate, ethyl alcohol, isopropyl alcohol, etc. is added to the polyurethane solution to adjust the concentration. Adjust viscosity and drying speed. Gloss control agents such as silica, coloring agents such as dyes and pigments, antioxidants, etc. can be added to the paint.
It is necessary to confirm that it does not inhibit adhesion before use.

Polyurethane resin [B] on the surface of the artificial leather base
The method of forming the film is not particularly limited, but it is preferably carried out using a gravure coater, a bar coater, a roll reverse coater, or the like. The coating amount of the polyurethane resin [B] is usually 2 to 50 g/m ² , preferably 5 to 30 g/m ² . If the amount applied is too small, sufficient adhesive strength cannot be obtained, and if the amount applied is too large, air permeability, moisture permeability, etc. will decrease, which is not preferable.

The method for manufacturing an artificial leather upper member according to the present invention includes:
It can be created through the usual processes of cutting, making uppers, lining, or bag stitching using a sewing machine. Although there are no particular limitations, after the lining or bag stitching is completed, the molten resin described below is applied. The solubility parameter of the artificial leather surface
After treatment with an organic solvent of 8.5 to 10, it is preferable to perform a bottoming process because adhesive strength can be increased. This is not only effective in removing contaminants adhering to the surface of artificial leather that can hinder adhesion, but also
It is thought that the effect of improving adhesion is due to swelling activation of the polyurethane resin [B] on the surface of the artificial leather by the organic solvent and partial compatibilization of the injection molded molten resin.

Solvents with a solubility parameter of 8.5 to 10.5 include ketone solvents such as methyl propyl ketone (8.9), methyl ethyl ketone (9.3), methyl isobutyl ketone (9.5), and acetone (9.8), butyl acetate (8.5), and ethyl acetate. (9.0), ester solvents such as methyl acetate (9.6), P-xylene (8.8),
Aromatic hydrocarbons such as toluene (8.9) and ethylbenzene (8.7), halogenated hydrocarbons such as trichlorethylene (9.3) and perchlorethylene (9.4),
Tetrahydrofuran (9.2), dioxane (10.1)
cyclic ethers such as, but from a hygienic point of view, ketone and ester solvents are most preferred.

Resins used for injection molding include vinyl chloride resins, vinyl chloride-vinylidene chloride copolymer resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-styrene-acrylonitrile copolymer resins, and other vinyl chloride-based resins.

It is possible to add plasticizers and fillers to these resins to give them the appropriate hardness for shoe soles, and it is also possible to add appropriate amounts of stabilizers such as pigments and antioxidants for coloring. It is.

The resin used for injection molding is melted at approximately 170 to 200°C, and then the artificial leather is injected into the upper member, which is processed into a shoe last, and into the mold of a matching sole mold. This method is a shoe sole molding method usually called an injection method, but the present invention can be applied to a general method of injection molding a molten resin that has been previously applied to a shoe sole.

e. Effects of the Invention As described above, according to the present invention, when manufacturing artificial leather shoes with a design, it is possible to attach soles by direct injection molding without using a primer, which can contribute to streamlining the process. However, the obtained shoes have excellent yellowing resistance and are of extremely great industrial significance.

f Examples Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that the following items are values measured by the method shown below. In addition, % and parts in the examples are based on weight unless otherwise specified.

() Thermal softening temperature After casting an organic solvent solution of polyurethane resin [A] or [B] on a glass plate, the solvent is dried and removed to form a film with a thickness of 0.15 mm. Cut this into a test piece with a width of 5 mm and a length of 20 mm, measure the weight, and convert it to the weight Wg per 1 m ² .

Next, this test piece was attached to a clamp with a gap of 10 mm, the upper part was fixed, and the lower part was freely movable, and a load of [W/10] g, including the weight of the clamp, was applied to the lower clamp. dimethylpolysiloxane (manufactured by Shin-Etsu Chemical)
KF-96) is installed inside the bus. This bath was heated at 2℃/
The temperature at which the test piece elongates by 10% is defined as the thermal softening temperature.

() Adhesive strength when dry In order to evaluate the adhesive strength between the injection molding resin and the artificial leather of the upper part, a test mold (5 mm thick, 20 cm vertically x 3 cm horizontally) was filled with injection molding resin.
Preheat in a flat plate heat press for 10 min at °C.

Next, the artificial leather for the adhesion test was cut into a length of 15 cm and a width of 15 cm.
Cut into 3.0cm pieces, attach 2.5cm wide cellophane tape to both ends so that the ends are aligned, place the artificial leather surface in contact with the preheated molding resin surface, and preheat for 30 seconds. Press at 100℃ with a press pressure of 2Kg/cm ² for 30 seconds, remove the pressure, and press with another flat plate cold press machine at the same press pressure for 100℃.
Cool under pressure until the temperature is below ℃.

Next, this test piece was taken out and cut to a width of 2 cm accurately, and then the non-adhesive portion of the end of the test piece was held in the upper and lower clamps using an Instron type tensile testing machine and peeled off at a speed of 50 mm/min. The peeling force until 4 cm peels off from the edge is recorded using a simultaneous recorder. Furthermore, the same test was repeated from one side of the test piece, and the average value of the peeling force recorded on the recorder was read, and this value was converted to a value per 1 cm width and was expressed as the adhesive strength (Kg/cm).

() Adhesive strength when wet Wet the test piece for measuring adhesive strength with solid soap ^* 0.1
% aqueous solution at 40°C for 24 hours and then measured by the method in (), the adhesive strength when wet is defined as the adhesive strength when wet.

* Shiseido Hanatsubaki Solid Soap Example 1 (1) Production of fibrous base material Polyethylene terephthalate with an intrinsic viscosity of 0.54 measured at 30°C in o-chlorophenol was
The undrawn yarn obtained by spinning at 270°C was drawn 2.6 times in hot water at 65°C to obtain a 1.8 de fiber with a shrinkage of 48% in hot water at 70°C. This is 51mm
Cut it out, put it on a card and create a web.
Needle punching was performed, and the material was further shrunk to 55% of its original area in warm water at 68°C. This was squeezed to a moisture content of 300%, and was simultaneously pressurized and dried in a drum pressure dryer at 130℃ to a thickness of 1.3 mm and an apparent density.
A nonwoven fabric of 0.30 g/cm ² was obtained.

(2) Manufacture of artificial leather substrate The nonwoven fabric obtained in (1) was impregnated with a dimethylformamide solution (15%) of polyurethane resin (Chrisbon 8766, manufactured by Dainippon Ink), squeezed, and coagulated by water immersion. Drain the water, then cast the same liquid on one side, place it on a conveyor net with a gentle slope, and add dimethylformamide.
After coagulating in a coagulation bath containing 10% at 40°C, it was washed with water to remove most of the solvent, and then dried.

(3) Manufacture of artificial leather undercoat substrate The surface of the artificial leather substrate obtained in (2) is coated with an undercoat having the composition shown below four times using a gravure roll (#110 mesh) to form a polyurethane undercoat film of approximately 10 μm. Artificial leather undercoated substrate with
I got (a).

Paint Crisbon 8766 30% dimethylformamide liquid
100 parts Methyl ethyl ketone 200 parts Titanium oxide 5 parts Irganox 1010 0.15 parts (4) Production of polyurethane resin [A] Polytetramethylene glycol (molecular weight 402)
634 parts of polyether ester diol with a molecular weight of 1150 and 3,5,
5-trimethyl-3-isocyanate with 306 parts of methylcyclohexyl isocyanate at 90°C.
The reaction was carried out for 90 minutes in a nitrogen stream. Next, dehydrated cold dimethylformamide was added and dissolved while stirring to make a 30% solution. A solution of 60 parts of propylene diamine in dimethylformamide (30% concentration) was successively added and polymerized for 6 hours while cooling to 30°C. The reaction was carried out, and finally 3 parts of dibutylamine was added to stop the reaction, and the viscosity measured at 20℃ was 10.
Got ten thousand centipoises of dope.

The resulting polymer in dimethylformamide
The intrinsic viscosity measured at 30°C was 0.84, and the heat softening temperature was 154°C.

(5) Manufacture of pattern-embossed artificial leather top-coated base Next, use this polyurethane resin [A] to create the following paint, and use a 110 mesh gravure roll to coat the surface of the artificial leather under-coated base (A). Apply twice to form a coating film of approximately 4 g/m ² ,
A top-coated artificial leather base [B] was created.

Topcoat [A] Example 1 Polyurethane resin [A] 100 parts Methyl ethyl ketone 100 parts Isopropyl alcohol 100 parts Titanium oxide 2.5 parts Silica 1.0 parts Irganox 0.15 parts Next, this artificial leather base [B] was stamped by plate making from calf leather from all directions. 150 embossing rolls
℃ and compressed to 40% of the thickness of the base while transferring the pattern onto the artificial leather base to create a pattern-embossed artificial leather overcoated base [C].

(6) Production of polyurethane resin [B] Polyoxypropylene glycol (molecular weight
400) and adipic acid through a condensation reaction
827 parts of polyether ester diol No. 2620 and 147 parts of 3,3,5-trimethyl-5-isocyanatemethylcyclohexyl isocyanate were reacted at 90°C for 90 minutes in a nitrogen stream. Next, add cold dehydrated dimethylformamide and dissolve while stirring to make a 30% solution.
- A solution of 26 parts of propylene diamine in dimethylformamide (concentration 30%) was added sequentially, the reaction was carried out for 6 hours while cooling to 30°C, and finally 3 parts of dibutylamine was added to stop the reaction, and the viscosity was measured at 20°C. Got 92,000 centipoints of dope.
30% of the resulting polymer in dimethylformamide
The intrinsic viscosity measured at °C was 0.82 and the heat softening temperature was 76 °C.

(7) Manufacture of artificial leather for upper parts Next, use this polyurethane resin [B] to prepare the following paint, and use a 110-mesh gravure roll to coat the surface of the pattern-embossed artificial leather topcoat base [C]. It was coated twice to form a coating film of 6 g/m ² .

Top coating [B] Example 1 Polyurethane resin [B] 100 parts Methyl ethyl ketone 100 parts Isopropyl alcohol 100 parts Titanium oxide 2.5 parts Silica 1.0 parts (8) Manufacture of shoes The obtained artificial leather was placed along the developed view of the upper of an athletic shoe. After cutting and sewing each part with a sewing machine, the insole material and bag stitching (California method) were performed to create the shoe upper part.

Next, set this in the mold of an injection molding machine,
Polyvinyl chloride resin (melting temperature: 175°C) was injected to form the sole of the shoe, and at the same time, the artificial leather of the upper part and the sole were bonded together. The obtained shoes were washed once a week and a wear test was performed for 3 months, but no abnormalities were observed.

The edges of the sole and upper parts of the same shoe were cut to a width of 1 cm, and the dry adhesive strength and wet adhesive strength were measured under the conditions described above, and the results were as follows.

Dry adhesive strength: 3.6 Kg/cm (broken surface, upper material fractured) Wet adhesive strength: 1.2 Kg/cm The polyvinyl chloride resin for injection molding used in Example 1 has the following composition.

Vinyl chloride resin (Shin-Etsu Chemical SC-500T)
100 parts Plasticizer (acrylonitrile 30% copolybutadiene) 25 parts Stabilizer American Cyanamid Antioxidant 2246 0.3 parts Dilaurylthiodipropionate
0.3 parts Filler Calcium carbonate 22 parts Blowing agent Diazo carbonamide 1.1 parts Example 2 (1) Production of polyurethane resin [B] Polybutylene copolymerized with 25 mol% of 2,2-dimethyl-1,3-propanediol 821 parts of adipate (molecular weight 2820), 130 parts of 3,5,5-trimethyl-3-isocyanate methylcyclohexyl isocyanate and 0.05 part of dibutyltin dilaurate were placed in a stirred reactor under a nitrogen stream.
The reaction was carried out at 70°C for 90 minutes. Next, while cooling this to 40°C, 2220 parts of dimethylformamide was added and dissolved to make a 30% homogeneous solution.
A solution of 49 parts of -trimethyl-3-amymethylcyclohexylamine dissolved in 114 parts of dimethylthyrumamide was successively added dropwise, and a chain elongation reaction was carried out for 4 hours while controlling the reaction temperature to 45±3°C. After that, 3.5 parts of di-n-butylamine was added to stop the reaction, the concentration was 30%, the viscosity measured at 20℃ was 96,000 centipoise, the intrinsic viscosity was 0.88, and the heat softening temperature was 102℃.
A polyurethane resin [B] was obtained.

(2) Manufacture of artificial leather for upper parts Next, use this to create the paint shown below.
Using a 110-mesh gravure roll, a coating film with a solid content of 12 g/m ² was formed on the surface of the pattern-embossed artificial leather top-coated substrate [C] prepared in Example 1-(5).

Top coating [B] Example 2 Polyurethane resin [B] 100 parts Methyl ethyl ketone 150 parts Isopropyl alcohol 50 parts Titanium oxide 2.5 parts Silica 1.0 parts (3) Manufacture of shoes The obtained artificial leather was applied at the same time as in Example 1-(8). ,
Sewn into a shoe last, create the upper part using the bag stitch method,
Shoes with soles were created by injecting vinyl chloride resin.
The side edges of the sole and upper of the obtained shoes were cut along the edges to a width of 1 cm, and the dry adhesive strength and wet adhesive strength were measured. The results obtained are as follows; the same shoes were washed once a week and a wear test was conducted for three months, but no abnormalities were observed.

Dry adhesive strength 3.8 Kg/cm (broken surface, upper material fracture) Wet adhesive strength 1.8 Kg/cm Example 3 Polybutylene adipate copolymerized with 10 mol% of 2,2-dimethyl-1,3-propanediol ( 736.4 parts (molecular weight: 1740), 221.8 parts of dicyclohexylmethane-4,4'-diisocyanate, and 0.05 parts of dibutyltin dilaurate were placed in a stirred reactor and reacted for 90 minutes at 70°C under a nitrogen stream. Then this
While cooling to 50°C, add 1434 parts of dimethylformamide to make a homogeneous solution with a concentration of 40%, then add 44 parts of diethylene glycol and 0.2 parts of dibutyltin dilaurate.
and 66 parts of dimethylformamide, and a chain extension reaction was carried out for 14 hours while controlling the reaction temperature at 65 to 68°C. Thereafter, 3.5 parts of di-n-butylamine was added to stop the reaction, and 833 parts of dimethylformamide was added to obtain a polyurethane resin with a concentration of 30%, a viscosity of 94,000 centipoise measured at 20°C, an intrinsic viscosity of 0.80, and a thermal softening point temperature of 65°C. .

This was applied to a pattern-embossed artificial leather top coat base [C] using the same formulation as in Example 1-(7).

A test piece was prepared using a flat plate press using the obtained artificial leather sole material of Example 1-(8) according to the adhesive strength measurement method described above, and then the dry adhesive strength and wet adhesive strength were measured. The measurement results were as follows.

Dry adhesive strength: 4.2 Kg/cm (ruptured surface, upper material fractured) Wet adhesive strength: 3.6 kg/cm (ruptured surface, upper material fractured) In addition, using this artificial leather for upper parts, Example 1
- After creating the upper part in the same manner as in (8), wipe the adhesive part with methyl ethyl ketone, dry it at room temperature for 10 minutes, set it in a mold under the same conditions as in Example 1-(8), and inject vinyl chloride resin into the shoe. At the same time as forming the sole, we glued it to the artificial leather of the upper. The shoes obtained were washed once a week and worn for 3 months, but no abnormalities were observed.

Comparative Example 1 Polymer diol used in Example 2 (molecular weight
2820) 821.0 parts, 3-isocyanatomethyl-3,
A reaction was carried out according to the method of Example 2-(1) using 130.1 parts of 5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) and 49.0 parts of 3,5,5-trimethyl-3-isocyanate methylcyclohexyl isocyanate.

The obtained polyurethane resin has an intrinsic viscosity of 0.750,
The thermal softening point temperature was 98°C. Example 1-(5)
A top-coated artificial leather base [B] was prepared using the polyurethane resin [A] instead of [A], and a pattern was embossed using the embossing roll used in Example 1-(5).
If the roll surface temperature is abnormal to 120°C, the surface resin will be significantly blocked, and 100°C will cause no blocking.
At temperatures below 0.degree. C., the pattern did not set and the appearance was extremely poor.

Comparative example 2 10 mol of 2,2-propane-1,3-diol
% copolymerized polybutylene adipate (molecular weight
1858) and 272.4 parts of 4,4'-diphenylmethane diisocyanate were reacted at 65°C with stirring under a nitrogen stream. Next, 1,421 parts of methylformamide was added and dissolved, and after cooling to 30°C, 1,2 parts of methylformamide was added and dissolved.
- A solution of propylene diamine in dimethylformamide (concentration 40%) was added dropwise and the reaction was carried out for 4 hours.
After adding an amount equivalent to 52.7 parts of 2-propylene diamine, 3.5 g of n-dibutylamine and 912 parts of dimethylformamide were added, and the mixture was further stirred for 1 hour.
The obtained polymer had a viscosity of 112,000 centipoise (concentration 30%, measured at 20°C), an intrinsic viscosity of 0.92, and a thermal softening point temperature of 172°C. The above polyurethane resin solution was diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol/dimethyl formamide=7/2/1 to give a concentration of 10%. After adding 5% fine particle silica to the polyurethane resin and uniformly dispersing it, the pattern-embossed top-coated artificial leather base [C] used in Example 1-(7) was coated with a gravure roll to approx.
15 g/m ² (solid content) was applied to make artificial leather for upper parts.

The adhesive strength of this was measured using the bottoming resin of Example 1-(8) according to the measurement method described above. As a result, the adhesive strength was 2.8 kg/cm when dry and 2.4 kg/cm when wet, which did not meet the practical adhesive strength. Also,
This product has discoloration due to light and gas from Actual Example 1 of this application.
It was worse than 3 and had no practical utility.

Claims (1)

[Scope of Claims] 1. After fitting a shoe upper made of artificial leather made of a fibrous base material and a rubber-like elastic material into a mold having a bottom mold that fits the upper, chloride is added into the mold. In manufacturing artificial leather shoes by injecting molten resin mainly made of vinyl resin to mold the sole and simultaneously bonding the sole to the upper member, the artificial leather is made of a fibrous base material and a rubber-like material. A film mainly composed of a polyurethane resin [A] having a repeating unit represented by the following general formula [] and a heat softening temperature of 130°C or higher is formed on the surface of an artificial leather base consisting of an elastic body, and then a design is formed. After applying a design to the surface by heating and pressurizing with a press mold, the surface is further coated with a polyurethane resin [B] having repeating units represented by the following general formula [] and having a heat softening temperature of 60 to 120°C. A method for manufacturing artificial leather shoes, characterized by using artificial leather formed with. [R ₁ is a divalent organic diisocyanate residue excluding the isocyanate group, R ₂ is a polymeric diol residue with a molecular weight of 800 or more excluding the hydrogen atom of the hydroxyl group, and R ₃ is a chain extender residue; A low molecular weight diol residue with a molecular weight of 200 or less excluding hydrogen atoms,
an aliphatic, alicyclic or aromatic diamine residue with one hydrogen atom removed from the amino group, or a hydrazine or hydrazine derivative residue with one hydrogen atom removed from the terminal amino group, l ₁ and m ₁ are 1 An integer greater than or equal to ] [R ₄ is an aliphatic or alicyclic organic diisocyanate residue, R ₅ is an aliphatic or alicyclic organic diisocyanate residue with a molecular weight of 1000 excluding the hydrogen atom of the hydroxyl group.
In the above polymeric diol residues, R ₆ is a chain extender residue, and is a low molecular weight diol residue with a molecular weight of 400 or less excluding the hydrogen atom of the hydroxyl group, or an aliphatic or aliphatic diol residue excluding one hydrogen atom of the amino group. Alicyclic diamine residue, l ₂ and m ₂ are integers of 1 or more. 2. Before injecting a molten resin mainly composed of vinyl chloride resin, the surface of the artificial leather of the shoe upper member that adheres to the resin when the molten resin is injected is treated with an organic solvent with a solubility parameter of 8.5 to 10.5. A method for manufacturing artificial leather shoes according to claim 1.