JPS59146602A - Production of artificial leather shoes - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 sheath material instead of natural leather, and at the same time, a rational shoe molding method has been developed, in which molten resin is injected into a shoe sole mold to form shoe soles. At the same time, is the instep made of artificial leather? The so-called direct injection tooling method, which involves bonding, has become popular. Synthetic rubber, unvulcanized rubber such as natural rubber, and polyvinyl chloride resin are commonly used as the resin for the eaves, but polyvinyl chloride resin is used for general-purpose shoes due to its low cost and short processing time. is often used...
It is. .

However, with conventional artificial floor leather, the adhesion between the resin and the flooring is not sufficient, so 1. After applying a pre-treatment agent called primer, which has a high affinity for both polycyclized vinyl resin and the surface of artificial leather, to the surface of the central artificial leather, it was necessary to injection mold the resin for flooring. Brimer contains a highly polar organic solvent and organic diisocyanate to improve adhesion, and if it adheres to surfaces other than the adhesive surface, it will discolor the artificial leather surface.

Therefore, it is necessary to carefully apply the molten resin to the parts that will adhere to it during injection molding, and this requires manual processing, making the work complicated. The disadvantage was that the costs involved were also large.

C1 Purpose of the Invention The present invention has been developed as a result of extensive research into a processing method for shoe soles that enables direct injection molding without the use of primers, which can cause such drawbacks. We have previously discovered and proposed a method for manufacturing shoes by direct eaves-attaching processing using artificial leather with a special polyurethane resin coating applied to the surface of the artificial leather base. However, with this method, if an attempt is made to apply a design by embossing the surface of the artificial leather with an embossing roll or the like having a design, the surface of the artificial leather will not be coated. a) The resin is easy to block, has strong adhesiveness and easily absorbs dust and dirt, and the surface σ) has a high coefficient of friction, making it difficult to sew when sewing using a sewing machine, etc. There was a problem that it was difficult to process because it was difficult to slip on metal plates such as tows and stars when fishing.

The inventors of the present invention conducted extensive studies to determine the adhesive strength in a dry state, which is required for practical adhesive strength, and the adhesive strength in a wet state, which is a problem when shoes are washed with warm water. It has an excellent design as a shoe, and is used for sewing, such as shoe processing.

The present invention has been achieved by making it possible to manufacture artificial leather shoes that eliminate the difficulty of slipping when worn.

d0 Structure of the Invention That is, the present invention is a shoe upper member made of artificial leather made of a fibrous base material and a rubber-like elastic body, which is fitted into a mold having a bottom mold that fits the upper member, and then inside the mold. In order to manufacture artificial leather shoes by injecting molten resin mainly composed of vinyl chloride resin to mold the sole and simultaneously bonding the sole to the upper part, the artificial leather is made of a fibrous base material and Forming a film mainly composed of a polyurethane resin (a) having a repeating level represented by the following general formula [■] and having a thermal softening temperature of 130°C or higher on the surface of an artificial leather base consisting of a rubber-like elastic body, Next, a design is applied to the surface by heating and pressing with a mold having a design, and then a polyurethane resin (( ) and polyvinyl chloride resin defined below (0 is polyurethane resin (river: vinyl chloride resin (C1 = 97
= 0.5 to 0.5 of the resin mixed at a weight ratio of 3 to 60:40
A method for manufacturing artificial leather shoes, characterized by using artificial leather formed with an s o i / rn' film.

0 0 0 011
II 11 ring-C-NH(-R,
-NHC-horse-C-NH-)-11horse-NI((-C-
m-〇 〇C-NH-R, -NII-) C'3...
CI) 1 0 0 Q 01 L~-〇-NH(-he-NHC-he-C-NH→121
[Tl
] Par( Polyvinyl chloride resin ((1 is the following general formula [1■]0CO
R? A polyvinyl chloride resin obtained by copolymerizing 3 to 45% by weight of a compound represented by the formula (2) or a compound represented by the following general formula (IV) with 2.9 to 37% by weight of a compound represented by the general formula (+n) It is a polyvinyl chloride resin copolymerized with o and i to 8 weights.

Artificial leather in duds refers to nonwovens made of synthetic fibers, natural fibers, etc., urethane fabrics made from fibrous base materials such as A-9 knitted fabrics, etc.
71 Elastomer, a resin with rubber-like elasticity such as synthetic rubber is attached, or at least one of these surfaces is coated with a resin mainly composed of polyutane elastomer so as to have a microporous structure. etc., and in parentheses,
Polyurethane, urethane resin, acrylic ester resin on the surface,
It refers to a product coated with a heat treatment mixture containing colorants such as cellulose resin, polyamide, resin, polyamino acid resin, etc. The method for manufacturing the artificial leather base is a conventionally known wet method.

This can be done by a dry method or the like.

The polyurethane resin matrix deposited on the surface of the artificial leather of the present invention has a square unit represented by the general formula [I], and the aliphatic diisocyanate used therein is Nato9.
6 g of microwaved isocyanate, hexame φreson iso diincyanate, phosphorus iso diincyanate (1) Linear organic diisocyanate, as alicyclic diisocyanate, cyclohexane incyanate, inroso diincyanate.

2-cyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, etc. in 1. In addition, aromatic diisocyanates include diphenylmethane diisocyanate, anene, -to, trile,
Among them, a naphate diisocyanate, a naphate diisocyanate, a xylylene diisocyanate, etc. are used.

Further, the polymer diol used in polyurethane a)+W(A)vc has hydroxyl groups at both ends and has a saccharide weight of 800 or more, preferably 1.000 to 3000.
Polyester glycols having a melting point of 70° C. or less, Holie, -Tyl glycol Polyester Ethelene glycol I. Polybutadiene glycol, etc., and the representative ones are polyethylene adipate, polybutylene adipate, and polycabrolactone glycol.

・Po 1. Dioxyethylene glycol, polyoxypropylene glycol, polyoxytetrame hand astragalus 1. :
vinegar. : I-ru, etc., or a mixture thereof can be used.A. As a soft segment material, those with a low crystallinity and a low melting point have better adhesion and are water resistant in order to maintain adhesive durability in practical use. Those with good degradability and resistance to microbial deterioration are preferred, such as butylene adipate copolymerized with 10 to 40 mol% of diethylene adipate, propyreso adipate, and 2.2-:)methyl-1,3-propanediol. ), pexamethyresoadipate obtained by copolymerizing 10 to 40 mol% of 2,2-dimethyl-x,3y7-/lovandiol.

Polyethylene glycol with an average molecular weight of 150-600.

Polypropylene glycol, copolymer of polytetramethylene glycol alone or mixed diol and adipic acid, polyester glycol with average molecular weight t150-600.

Polypropylene glycol, polytetramethane, and two-handed range glycol as a chain extender.

Tetramethylene glycol, 1.5-bentanediol, 1.6-hexanediol, diethylene glycol,
Low molecular weight alcohols such as triethylene glycol, aliphatic diamines such as propylene diamine, hexamethylene diamine, and inphorone diamine.

Cyclohexylene diamine, 4.4'-diaminodicyclohexylmethane, 4.4'-diakylene-3,3'
-Alicyclic di-amines such as dimethyldicyclohegycylmethane, hydrazines such as methylhydrazine, phenylhydrazine, benzylhydrazine, dicarboxylic acids such as 7-dipic acid, sebacic acid, glycine□, alanine, and amino acid hydrazides. It can be used.

In order to achieve the object of the present invention, the polyurethane resin must have a heat softening temperature of 130° C. or higher. 1
If the temperature is less than 30°C, blocking tends to occur during embossing for design, which is unsuitable. The heat softening temperature of this polyurethane resin (3) varies depending on the composition of the raw materials used for polymerization of the polyurethane resin, but the heat softening temperature is determined by the ratio of the number of moles of the chain extender to the number of moles of the polymeric diol (R
It can be controlled by changing 17' (abbreviated as 17'), and the thermal softening temperature increases by increasing 17'.

To form a polyurethane resin film on an artificial leather substrate, prepare a volatile organic solvent solution of polyurethane resin,
After adjusting the viscosity to 50 to 500 cps, it is applied by gravure transfer method, reverse roll coating method, chi-coat method, spray method, etc., or by applying it to release paper etc. and drying or adhering without drying. 3. Coloring agents, stabilizers, gloss modifiers, etc. may be added to the organic solvent solution containing the polyurethane resin. Bol
; The coating amount of the urethane resin is 2 to 50 g/m' in terms of solid content, preferably 5 to 20 g/m'.

Next, the design is transferred by heating and pressing an embossing roll or Esoboss board with the design. Polyurethane resin (
In order to sufficiently incorporate a design into an artificial leather base coated with M, the temperature, pressure and compression time during embossing may be adjusted respectively.

Next, a film of a mixed resin consisting of polyurethane resin (8) and polyvinyl chloride resin (C1) is formed on the design.

The polyurethane resin (polyurethane resin field) has a repeating unit represented by the above general formula (ff), and the aliphatic diincyanate used therein is a linear chain such as tetramethylene diisocyanate, hexamethylene diisocyanate, lysine incyanate, etc. Cyclohexane diisocyanate and inholone diisocyanate are examples of the alicyclic diinsocyanate.

These include dicyclohexylmethane-4,4'-diisocyanate and dicyclohexyldimethylmethane-4,4'-diisocyanate.゛Polyurethane resin (I3)
The reason why the diincyanate described above is necessary is that the aromatic diisocyanate normally used in the production of H+) urethane resin not only has poor yellowing resistance, but also has a high resistance to aromatic diisocyanate and chain extender. This is because the crystal melting point of the hard segment of the polyurethane elastomer made of the material becomes too high, and the softening activity of the hard segment when it comes into contact with the heated and melted garden resin is poor, 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 diincyanate.

In addition, the polymeric diol used for polyurethane resin (Bl) has hydroxyl groups at both ends, has a molecular weight of 1000 or more, preferably 1200 to 3000, and has a melting point of 70°C.
Polyester Glyfur, polyether Glyfur, polyether ester glycol with lower melting point.

These include polybutane diene 11-col, representative examples of which are polyethylene adipate, polybutylene adipate, polycaprolactone glycol, and polyoxyethylene glycol.

Polyoxypropylene glycol, polyoxytetramethylene glycol, etc. or a mixture thereof can be used, but soft segments with low crystallinity and low melting point have better adhesion and maintain contact layer durability in practical use. Those having good hydrolysis resistance and microbial deterioration resistance are preferred, and butylene adipate is a butylene adipate obtained by copolymerizing 10 to 40 mol% of diethylene adipate, butylene adipate, and 2,2-dimethyl-1,3-propanediol.

2.2-dimeryl 1,3-propanediol from 10 to
40 mol% copolymerized hexamethylene adipate, average molecule! □150 to 600 Bolier hand gestures,
Polypropylene glycol, polytetramethylene glycol alone or a copolymer of mixed diol and adipic acid, polyethylene glycol and polypropylene glycol having an average molecular weight of 150 to 600.

Further, the chain extender is ethylene glycol.

Tetramethylene glycol, 1.5-bentanediol, 1.6-hexanediol, diethylene glycol,
Low molecular weight diols such as triethylene glycol, aliphatic diamines such as ethylene diamine, propylene diamine, hexamethylene diamine, and inphorone diamine.

Cyclohexylene diamine, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-
Alicyclic diamines such as dimethyldicyclohexylmethane,
Hydrazine such as methylhydrazine, phenylhydrazine and benzylhydrazine, dicarboxylic acids such as adipic acid and sebacic acid, glycine □, hydrazides of amino acids such as alanine, etc. can be used.

The thermal softening point temperature of the fat (B) needs to be 60 to 120°C, preferably 80 to 110°C. If the heat softening point temperature exceeds 120°C, the heat softening activation by the molten gardening resin will be poor, and the adhesiveness with the molten resin will be poor (very unfavorable).If the heat softening point temperature is lower than 60°C, The insole and upper leather are sewn using a sewing machine, which is known as the California method, which softens the workability by heat from a wiper when hanging the shoes, heat from the dry heat setting process, etc. It is preferable to take the method of

The thermal softening temperature of polyurethane resin is determined by the composition of the hard segment consisting of diincyanate and chain extender, the proportion of the eight-dos segment in the total resin, and the molecular chain length of the polyurethane resin. In order to maintain the above range, 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 diincyanate content and the amount of chain extender, and by increasing the degree of polymerization of the polyurethane resin.

In addition, regarding the composition of diincyanate, those with high crystallinity and rigidity of the molecular chain have a higher softening point, and the chain extender also has high crystallinity, high rigidity of the molecular chain, and hydrogen bonding. The higher the density, the higher it will rise.

The method for producing the polyurethane resin (B) is not limited, but it is possible to prepare the polymer diol and diincyanate so that the value of [number of moles of diisocyanate]/[number of moles of polymer diol] is 2 or more, and to prepare the polyurethane resin (B) without a solvent or with incyanate. A preferred method is to react in an organic solvent that has no reactivity to the polymer to prepare a prepolymer having an isocyanate group at the end, and then add a chain extender to carry out the chain extension reaction. Chain extension reaction uses dimethylformamide and dimethylacetamide.

Hexamyl phosphoramide, dimethyl sulfoxide,
This can be carried out in a single or mixed solvent such as diekylformamide, dioxane, and tetrahtomifuran.

In the present invention, polyvinyl chloride resin (
0 is specifically vinyl acetate, vinylb4bio$-
), vinyl monomers such as vinyl butyrate from 3 to 45
There are polyvinyl chloride resins that are copolymerized in weight percent.

If the copolymerization ratio is less than 3% by weight, the polyvinyl chloride resin has strong characteristics and is difficult to dissolve in coating solvents, and there are disadvantages such as crystallization during the solvent removal process and insufficient adhesion strength. is 45 times! :%, the thermal softening temperature decreases too much to be practical. Copolymerization ratio is preferably 5 to 35
Copolymerized polycrystalline heel ft41
Among these, the most preferable is vinyl acedate from 5 to 3.
It is a 5% copolymerized product (Z).

It is also effective to copolymerize maleic acid or maleic acid ester as part of the 2G vinyl monomer, and maleic acid or maleic acid ester is also effective.
It is preferable to copolymerize M%, preferably 1 to 6% by weight. The most preferred three-dimensional copolymer is a copolymer of 3 to 35% by weight of vinyl acetate and 1 to 6% by weight of maleic acid, methyl maleate, or ethyl maleate.

Polyurethane resin (B): Vinyl 14ide resin (C1
The mixing ratio (by weight) must be in the range of 97:3 to 60:40, most preferably 90:, 10 to
70:30.

If the amount of vinyl chloride resin (C) is less than 3% by weight, the added amount will be small and the addition effect will be achieved.On the other hand, if it exceeds 40% by weight, the amount of vinyl chloride resin in the polyurethane resin (B) will be excessive and the viscosity-N property will decrease. Although the processability is improved, the bending resistance at low temperatures is decreased, which is not preferable. polyurethane resin) and vinyl chloride resin (C1 is a mixed paint by dissolving both resins in the ial solvent.The solvents used are the above-mentioned polyurethane resin (cinnochlorformamide, which is a solvent for 13+),
Nmetal acetamide, hegizamethylphosphoramide,
Add appropriate amounts of low-boiling organic solvents such as acetone, methyl ethyl ketone, diethyl ketone, and methyl imbutyl ketone in addition to geosaisan and tetrahtomifuran to adjust the concentration, viscosity, and drying speed = in the paint. Gloss control agents such as silica, coloring agents such as dyes and pigments, antioxidants, etc. can be added, but it is necessary to use them after making sure that they do not impede adhesion.

The method for forming the mixed resin coating on the surface of the artificial leather substrate is not particularly limited, but it is preferably carried out using a gravure coater, a bar coater, a roll reverse footer, or the like. The coating R of the resin consisting of Boliu 1/tan resin (Peng) and vinyl chloride resin (C1) is usually 1 to 509/V, preferably 5 to 309/717'. If the coating amount is small, the adhesive strength If a sufficient amount is not obtained or the coating amount is too large, air permeability, moisture permeability, etc. will decrease, which is not preferable.

The method of manufacturing the artificial leather upper part of the invention is particularly limited because it can be made through the usual steps of cutting, making the upper, and sewing the bag with a sewing machine. Although it has not been done, after the fishing or bag stitching is completed,
It is preferable that the surface of the artificial leather in the area to be contacted with the 1M melted resin described below is treated with an organic solvent having a solubility parameter of 8.5 to 10 or acid-processed to increase the strength of the contact layer. This is not only effective in removing contaminants that are a layer on the surface of the artificial leather and becomes a hindrance to the removal of debris, but also due to the swelling activation of the polyurethane resin (Bl) on the surface of the artificial leather by the organic solvent and the partial phase formation of the injection molded molten resin. Density due to solubilization
It is thought that this has the effect of improving f-characteristics.

Specifically, the solvent with a solubility parameter of 8.5 to 10.5 is methyl propyl ketone (8,9).

Ketone solvents such as methyl ethyl ketone (9,3), methyl isobutyl ketone (9,5), acetone (9,8), butyl acetate (S, S), ethyl acetate (9,0), methyl acetate (9) , 6), P-xylene (8
,8),) luene (8,9), two-handed rubenzene (8,7
), aromatic hydrocarbons such as trichlorethylene (9,3
).

halogenated hydrocarbons such as perchloroethylene (9,4), tetanhydrofuran (9,2);

Examples include cyclic ethers such as dioxane (10,1), but ketone and ester solvents are most preferred from a hygienic standpoint.

The resin used for the injection molding includes vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, and vinyl chloride-vinyl acetate copolymer resin.

Examples include those based on chlorinated beer, such as vinyl chloride-styrene-acrylonitrile copolymer resin.

It is possible to add plasticizers and fillers to these resin pressures 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 injected into the mold of an upper member made of artificial leather and processed into a shoe last, and a shoe sole mold that matches the upper member. 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 is 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 brimer, which can greatly 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.

1) After casting an organic solvent solution of heat-softening temperature polyuntane resin (5) or (B) onto a glass plate, the solvent is removed by drying to a thickness of 0.15
Create M film.

This is cut into a test piece with a width s m and a length of 20 m, the weight of which is measured and converted to the weight Wg per shrimp.

Next, this test piece was attached to a clamp with a gap of tOW, with the upper part fixed and the lower part freely movable.
CW/lO), including the clamp weight on the lower clamp, 9
(With a DM load applied, this is placed in a dimethylpolysiloxane (Shin-Etsu Chemical HKF-96) bath.The bath is heated at a rate of 2℃/trend, and the temperature at which the test piece elongates by 10% is reached by heat softening. Temperature.

11) In order to evaluate the adhesion strength between the strong injection molding resin and the artificial leather of the upper part when dry, a test casting fj1 (thickness 5m, length 20α x width 3cm) was filled with injection molding resin and heated to 10℃ at ISO℃. Preheat in a flat plate heat press for a minute.

Next, a piece of artificial leather for the imitation test with a length of 15 cm, @3
．． Cut it into 0cm pieces, stick cellophane tape with a width of 2.57m on both ends so that the ends meet, and place it on the preheated molding resin surface so that the artificial leather garment is in contact with it.
After preheating for 30 seconds, press at 100℃ and press pressure 2K.
9/cr After pressurizing for 130 seconds, it is removed, taken out, and cooled under pressure in another flat plate cold press machine at the same pressing pressure until the temperature reaches 100°C or less.

Next, take this test piece and cut it accurately to a width of 2cl11, and then use an Instrosofi (71J tensile tester) to grasp the non-adhesive portions of the test piece with the upper and lower clamps at 50.
．． Peeling was performed at a speed of 7 m, and the peeling force until 4 CrrL was peeled from the edge was 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 the value obtained by converting this value per lcR width was expressed as the adhesive strength (kl?/bi).

111) Adhesive strength when wet The above-mentioned test piece for measuring adhesive strength was soaked in a 0.1% solid stone care aqueous solution and immersed at 40°C for 24 hours, and then the adhesive strength measured by the method of 11) was defined as the adhesive strength when wet.

*Shiseido Hanatsubaki Solid Stone Ken HIII (1) Production of fibrous base material Polyethylene terephthalate with an intrinsic viscosity of 0.54 measured at 30°C in OCR phenol was 271'1
℃, and the resulting undrawn yarn was placed in warm water at 65℃ for 2.
A 1,8'de fiber was drawn by 6 times and had a shrinkage of 48% in hot water at 70°C. This was cut into 5111111 pieces, carded to create a web, subjected to 21 dollar bath soching, and further shrunk to 55% of the original area in hot water at 68°C. Reduce this to 300% water content and 1
Pressure and drying were carried out simultaneously in a drum pressure dryer at 30° C. to obtain a nonwoven fabric with a thickness of 1.3” and an apparent density of 3.0 and 9/2.

The non-woven fabric obtained by fi+ was impregnated with a dimethylformamide solution (15%) of polyurethane resin (Chris Boso 8766 Dainippon Ink style), squeezed and coagulated by immersion in water, the surface was drained, and the same solution was further soaked. It was cast on one side, placed on a conveyor net with loose In, coagulated in a 40°C coagulation bath containing 10% dimethylformamide, washed with water to remove most of the solvent, and then dried.

(3) Manufacture of artificial leather undercoat substrate (apply undercoat paint having the following composition on the surface of the artificial leather substrate obtained in 21 using a gravure roll (#110 mesh)
An artificial leather undercoat substrate (A) having a polyurethane undercoat film of about 10 μm was obtained by coating the base coat four times.

Paint Crisbon 8766 30% dimethylformamide 1
100 parts methyl ethyl ketone
200 parts methane oxide 5 parts Irganox 1 oio, is part 634 parts of polyether ester diol with a molecular weight of 111,150 which is a condensation reaction of polytetramethylene dalycol (molecular weight 402) and adipic acid and 3.5.5-) riftyl- The mixture was reacted with 306 parts of 3-incyanatomethylcyclohexyl isocyanate at 90° C. for 90 minutes in a nitrogen stream. Then, it was dehydrated, and one drop of cold dimethylform 7mide was added and dissolved while stirring to make a 30% solution for 7 nights.
Propylenesia S solo 0 parts dimethylformamide ff
+ liquid (concentration 30%) was added sequentially, and the polymerization reaction was carried out for 6 hours while cooling to 30°C. Finally, 3 parts of dibutylamine was added to stop the reaction, resulting in a dope with a viscosity of 100,000 centipoise measured at 20°C. I got it.

The obtained polymer had an intrinsic viscosity of 0.84 and a heat softening temperature of 154°C at 30°C in dimethylformamide.

Next, use this polyurethane resin (5) to
Prepare the material I and finish the undercoating using a gravure roll of 10 mesh.Apply it twice to the surface of the artificial leather undercoat base (A) to form a coating film of about 4 g/m'', and apply the topcoat artificial leather. Top coat (5) prepared from leather substrate (I:I) Example 1 Polyurethane resin (A) 1
00N methyl ether ketone 100
Part isobutyl alcohol 100 parts Titanium oxide 2.5 parts Si
mosquito
1. Part O Irga/Tux fl, Part 15 Next, this artificial leather base (B) is made from calf hexagonal buffed leather using an embossing roll, heated to 150°C, compressed to 40% of the thickness of the base, and shaped into a pattern. was transferred onto the artificial leather substrate to create an artificial leather overcoat substrate ←→ with the pattern pressed.

827 parts of polyether ester diol with a molecular weight of 2620 obtained by condensation reaction of polyoxypropylene glycol (molecular weight 400) and adipic acid and 3.5.5 parts of polyoxypropylene glycol (molecular weight 400) and adipic acid and The mixture was reacted with 147 parts of Ane'-te at 90°C for 90 minutes in a nitrogen stream. Then, dehydrated cold dimethylformamide was added and dissolved with stirring to make a 30% solution, and then 1,2-propylene A solution of 26 parts of diamine in dimethylformamide (concentration 30%) was added sequentially, and the reaction was carried out for 61 hours while cooling to 30°C. Finally, 3 parts of dibutylamine was added to stop the reaction, and the viscosity measured at 20°C was 9.2. The obtained polymer had an intrinsic viscosity of 0.8 as measured at 30°C in dimethylformamide.
2, and the heat softening temperature was 76°C.

Next, polyvinyl chloride resins copolymerized with 7%, 25%, 35%, and 50% vinyl acetate, respectively, were dissolved in 268 parts of methyl ethyl ketone in the proportions shown in Table 1, and then the polyurethane resins copolymerized previously were dissolved. (5) 100 copies (30% A degree)
After uniformly mixing, 2.5 parts of titanium oxide, 1.0 part of silica, and 0.15 parts of Irganox 1010 were added and mixed using a homomixer to prepare a top coat.

The resulting paint was applied to the surface of the above-mentioned pattern-embossed artificial leather top-coated base (c) using a 110 mesh beer roll and dried to form a coating film of about 8.9/vl.

The artificial leather obtained in step (4) was cut along the developed view of the upper of the athletic shoe, each part was sewn using a sewing machine, and then sewn to the insole using a bag stitch method. In Example 1-■, there were no particular problems in practical use, except that the sewing machine was slightly slippery. This was then set in a mold of an injection molding machine, and polyvinyl chloride resin (melting temperature: 180° C.) was injected to form the sole, and at the same time, the artificial leather of the upper member and the sole were bonded.

The obtained shoes were washed once a week and a wear test was conducted for 3 months, but no defects were observed.

The dry adhesion strength and wet adhesion strength of the same artificial leather as described above were measured using the same polyvinyl chloride resin, and as shown in Table 2, the trowels met the practical adhesive strength.

The polyvinyl chloride resin for injection molding used in Example 1 had the following composition.

Vinyl chloride resin (Shin-Etsu Chemical 5O-500T) 100
1 part Plasticizer (30% acrylonitrile copolymerized polybutadiene) 25 parts Stabilizer American Cyanamid Co., Ltd. Antioxidant 2246 0.3 parts Dilaurylthiodipropionate 0.3 parts Light-filling agent Calcium carbonate 22 parts Blowing agent Diazo carbonamide 1 .1 part Table 2 Example 2 Polyvinyl chloride resin 15 copolymerized with 25% vinyl acetate
was dissolved in 335 parts of methyl ethyl ketone, mixed with 100 parts of the same polyurethane resin [B3] used in Example 1, and further mixed with 2.5 parts of titanium oxide, 0 parts of silica,
0.15 part of Irganox 1010 was added and mixed uniformly to prepare a top coat.

Using this, it was coated on an artificial leather top coat base (c) in the same manner as in Example 1-2 to produce artificial leather. The characteristics of each of the obtained artificial leathers are also shown in Table 2.

Comparative Example 1 Artificial leather was prepared using only the same polyurethane resin (l) as used in Example 1, and other conditions were the same as in Example 1, and evaluated under the same conditions.

The properties of the obtained artificial leather are shown in Table 2.Although the adhesive strength was sufficient, the surface friction coefficient was large and the stitching was difficult with a sewing machine, resulting in poor workability.

Comparative Example 2 Using a vinyl acetate/vinyl chloride copolymer resin obtained by copolymerizing 50% vinyl acetate, artificial leather was prepared and evaluated under the same conditions as in Example 1-■.

The evaluation results are shown in Table 2. Although the adhesive force is sufficient, the coefficient of friction when hot is high, 'P~, and the slippage with Towlaster's wiper (surface temperature approximately 78°C) is poor (hanging cost is low). It's getting longer, and the skein of the toe part is poorly organized.

Example 3 2,2-dimethyl-1,3-probadadiol 25
821 parts of polybutylene ambate (molecular weight 2820) copolymerized with mo1%, 3,5.5-) Limete Roux 3-
Incyanate cyclohexyl isocyanate 1
30 parts and 0.05 part of dibutyl tin dilaure were reacted for 90 minutes at 70°C under a nitrogen stream in a stirred reactor. Then, while cooling this to 40°C, dimethylformamide 22
After adding 20 parts and dissolving it to make a 30% homogeneous solution,
A solution of 49 parts of 3,5.5-trimethyl-3-7minomethylcyclohexylamine dissolved in 114 parts of dimethylformamide was added dropwise to 45 parts, and a chain extension reaction was carried out for 4 hours while controlling the reaction temperature to 3°C. . After that, 3.5 parts of di-n-butylamine was added to stop the reaction, and the concentration was 30%.
Viscosity measured at 20°C: 96,000 inch poise.

Intrinsic viscosity 0.88. A polyurethane resin () having a heat softening temperature of 102°C was obtained.

Next, a vinyl acetate-maleic acid-vinyl chloride ternary copolymer resin having the composition shown in Table 3 was dissolved in an 8/2 mixed solvent of beef ethyl ketone/dimethylformamide to form a 20% solution.

1 Add 10 parts of each of the above vinyl acetate-maleic acid-vinyl chloride copolymer resin solutions to 100 parts of each MfT polyurethane resin solution and mix, and add 5% of fine particle silica to the total amount of resin. Uniformly dispersed using a homomixer.

Artificial leather substrate (c) I using the obtained paint in Example 1
c IJ birth roll coder approx. 3011/n?
(solid content) was applied.

The adhesive strength of the obtained artificial leather to the garden vinyl chloride resin used in Example 1 was measured according to the above-mentioned measuring method.

As shown in Table 4, the obtained artificial leather had a low surface friction coefficient and an adhesion strength that met a practical level.

Comparative Example 3 In Examples 3-1 to 3, artificial leather was prepared and evaluated under the same conditions as in Example 3 using only polyurethane resin without using vinyl acetate-maleic acid-vinyl chloride resin. The results are also listed in Table 4. The obtained artificial leather had a higher surface friction coefficient and inferior workability than the unexploded product.

Comparison gA+ 4 Artificial leather was prepared and evaluated in the same manner as in Example 3, except that a copolymerized form of vinyl acetate and 30% maleic acid was used, and a phosphoric acid-vinyl chloride resin was used. As shown in Table 4, the obtained artificial leather had sufficient dry adhesive strength, but the wet adhesive strength tended to decrease.

Comparative Example 5 The polymer diol used in Example 3 (molecular weight 2820
) 82'l, 0 parts, 3-incyanate beef roux 3,5
．． 5-) IJ methylcyclohexyl isocyanate (isophoso diisocyanate) x 30.1 parts, 3
, 5.5 =-) dimethyl-3-incyanate A reaction was carried out according to the method of Example 2 using 49.0 parts of cyclohexyl isocyanate.

The obtained polyurethane resin had an intrinsic viscosity of 0,750° and a thermal softening point temperature of 98°C. This was used in place of the polyurethane resin (4) of Example 1, and the top-coated artificial leather base (I
:+) was created.

This was pattern-pressed using esobothronil used in Example 1, but when the surface temperature of the a-ru was 120°C or higher, the surface resin was significantly blocked, and blocking did not occur.
At temperatures below 00°C, the pattern was not sharp and the appearance was extremely poor.

Comparative Example 6 Polystyrene adipate (molecular lk 1.858
) was used as the polymer diol, and this polyol 67
4.9 parts of 4.4'-diphenylmethane diincyane) were reacted at 65° C. with stirring under a nitrogen stream. Next, 1,421 parts of dimethylformamide was added and dissolved, and the mixture was cooled to 30°C. A solution of 1,2-propylenediamine in dimethylformamide (concentration: io%) was then added dropwise to react for 4 hours. After adding the equivalent of 7 parts, 3.5 g of dibutylamine and dimethylformamide were added.

912 parts were added and further stirred for 1 hour. The resulting polymer had a viscosity of 112,000 cps/30%.

The intrinsic viscosity at 20°C was 0.92, and the thermal softening point temperature was 172°C. The above polyurethane resin solution was mixed with methyl ethyl ketone/inpropyl alcohol/dimethylformamide=
It was diluted with a mixed solvent of 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 was coated using a gravure roll.
519/rrl (solid content) was applied.

The adhesive strength of this was measured using the bottoming resin of Example 1 according to the measurement method described above. As a result, the adhesive strength was 2.8 when dry.
Kg/(!lrL, wet 0.2 kll/C
It was AR and did not meet the practical adhesive strength. The color change due to light and gas is how many layers ~ 2 ~
■It was worse and had less practicality.

Claims (1)

[Scope of Claims] l After fitting a shoe upper member made of artificial leather made of a fiber leather base material and a rubber-like elastic body into a mold having a bottom mold that fits the upper member, chloride is added to the inside of the mold. In manufacturing artificial leather shoes by injecting molten resin, mainly vinyl resin, to mold the sole and simultaneously bonding the sole with the core, the artificial leather is made of a fibrous base material and a rubber-like elastic material. On the surface of an artificial leather base consisting of After heating and pressurizing with a press mold to impart a design to its surface, a polyurethane resin tB) having a repeating unit represented by the following general formula (n) and a heat softening temperature of 60 to 120°C on its surface and defined below. Polyvinyl chloride resin (C) to polyurethane resin LB): Vinyl chloride resin (C): 97:3-6
0.5 to 50 g of resin mixed in a weight ratio of 6:40/
0 0 0 01 [He-C-NH (-R, -NHC-He-C-NH-1,
Tchi-NH, (c--1Q 0 C-NH-equal-NH part C]... CI) Cylinder L 4. and ml is an integer of 1 or more. of(
) 0゛1 C-NH- to -NH portion C''+... CI) Polyvinyl chloride resin (C) contains 3 to 45% by weight of a compound defined by the following general formula Cm) Polymerized polyvinyl chloride resin or compound represented by the above general formula [■'] 2.9
It is a polyvinyl chloride resin having a total weight of 37% by weight and having the following general formula CIVI. 2. Pre-pressure of injecting a molten resin made from chlorinated beer wood. A method for producing shoes made of artificial leather made of Ikkomon material, which is bonded to the resin when the molten resin is injected.