JPS5838155A - Rubber cloth and its manufacture - 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 The present invention relates to a rubber-coated cloth useful as a material for rubber boats, raincoats, mats, etc., and a method for producing the same.

Conventionally, rubber-coated cloth is produced by coating rubber on an arbitrary base material, and pasting a thin rubber film separated from a calender on top of this.
A thin rubber skin is replaced on the base material by a method called the so-called calendar topping method, in which the rubber is laminated by pressure bonding using a pressure roll, etc.
- The rubber was laminated, and then the rubber *** was sprayed with @, brushed, and then vulcanized to produce a product.

However, in order to make rubber-coated cloth using this calendar topping method, one OSE equipment called a calendar is required, and a multi-step process including a step of lowering the rubber St., a step of calender topping, and a step of vulcanization are required. It is complicated, requires a huge amount of capital investment, requires a large installation space, and requires a large number of workers.

Furthermore, the vulcanization process S required heating to at least 150'C or more, and was one of the processes that consumed a lot of energy. In addition, it is common for rubberized fabrics to have a lubricity property by scattering powder on the surface to prevent the rubberized fabrics from sticking to each other and to maintain a non-sticky feel. The adhesion to the rubberized fabric was poor, and sufficient dusting force could not be expected.

Furthermore, over time, when it is put into practical use as a product, the powder from the φ-split cloth will fall off and its slipperiness will be lost.

The conventional method is to dissolve the rubber compound in a solvent, apply the dissolved rubber compound onto the base material, heat it in a heating oven, etc. to volatilize the solvent, and then remove the rubber compound from the base material.
Rubberized fabrics have also been produced by forming a rubber layer thereon, scattering powder on the rubber layer, performing a brushing session, and then vulcanizing at a high temperature of 150° C. or higher.

However, like the calendar topping method, this method also requires a vulcanization step that requires a high attenuation rate and consumes a large amount of energy. The rHJ turtle with flour dusting lubricity was also similar to that produced by the calendar topping method.

Furthermore, in this method, it was difficult to produce long lengths of KI9L, and it was difficult to obtain a satisfactory product because the rubber compound melted in advance was difficult to produce.

In addition, when a thick rubber Ml is provided on a base material, the amount of silver agent in the rubber compound melt is as large as 50X or more. It has the disadvantage that it has to be applied thinly over several doses, which can lead to product failure due to the occurrence of product defects.

The present invention has been made with the aim of solving these drawbacks of conventional rubberized fabrics and methods of manufacturing the same.

That is, at least one piece WJ of the rubber-covered fabric and base material of the present invention
It is made by laminating a reaction product of K rubber and polyinocyanate.

Further, the method for manufacturing a rubberized fabric according to the present invention is to mix and discharge liquid rubber and polyisocyanate in a multi-continuous manner using a mixing and discharging machine, and directly apply m! to the base material. Either cloth or the base material (
It is made by transferring Ik cloth and laminating it.

The liquid rubber in the present invention exhibits wave behavior at home temperature, and has a carboxyl group, a hydroxyl group, a mercapto group, a halogen atom, an amine 7 group, and an aziridino group at the molecular terminal.

Polybutadiene, polyimprene, polychloroprene, )゛tadiene-inoprene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene with an average molecular weight of 500 to 10,000 and having a crosslinkable functional group such as an epoxy group These are telechelic liquid rubbers such as copolymers, and these pots may be used alone or in combination of two or more types.

In the liquid rubber, liquid polybutadiene having a hydroxyl group at the end of the molecule and highly reactive liquid polybutadiene having an allyl type primary one at the end of the molecule is particularly preferred.

The liquid rubber of the present invention further contains fillers and water agents as compounding components that are generally used to improve physical properties.

Reaction w4@ agent, crosslinking agent, anti-aging agent, process eugelethanization catalyst, blend polyol [color M.

It can be used by blending solvents and the like.

The above-mentioned fillers include calcium carbonate, activated calcium carbonate, clay, white carbon, various types of curlew, aluminum hydroxide, and zinc white.

Aluminum sulfate, calcium sulfate, Merck, Ganic acid! Gnesium, mica, asbestos, pumice powder.

-tmle end e wood 1m, col/powder, PYmuiin,
All fillers that are generally blended into solid rubber, such as cellulose powder, can be used, and these can be used alone or in twos.
It may be used in combination with Class A or above. Addition amount is liquid rubber 1
300 parts by weight or less, preferably Fii
Ω~20Q] 1iJi part is good.

Foaming may occur in the product due to water absorbed by the filler, but to prevent this foaming, we use quicklime, silane coupling NJ, titanate coupling agents, various types of Molecule Sweep, anhydrous calcium sulfate, Water-absorbing fillers with high water-absorbing properties such as copper sulfate, magnesium sulfate, sodium sulfate, activated alumina, Arashitoshi potassium, and magnesium oxide can be used, and these can be used in single w1 or 211fj
The above may be used in combination.

By using this water-absorbing filler, it is possible to prevent foaming caused by water adsorbed by the filler, and a good rubberized fabric can be obtained.

Examples of reaction modifiers include acids such as sulfuric acid, hydrochloric acid, acetic acid, tartaric acid, benzoic acid, formic acid, stearic acid, phosphoric acid, chelic acid, maleic acid, malic acid, hexamaric acid, and salicylic acid, sodium hydroxide, and potassium hydroxide. , alkalis such as sodium dioxylate can be used. These reaction regulators may be used alone or in combination of two or more of the acids and alkalis.* *SAcids and alkalis a should not be used at the same time.

The amount of the reaction regulator added to the liquid rubber is 50 parts by weight or less, preferably in the range of F11 to 10 parts by weight, per 100 parts by weight of the liquid rubber.

This reaction regulator accelerates or delays the urethanization reaction between the liquid rubber and the polyisocyanate.

As a crosslinking agent, a low-molecular hydroxyl compound having Fi2 or higher functionality can be used. Examples include 1.47'tanediol and 1,5 benmethol.

Polymer glycol, diethylene glycol, 1゜6 hexanediol, neopentyl/IJ co-h.

Glycerin, jetanolamine, triethanolamine, trimethylolpropane, hydroquinone, bisphenol, M, M, bis(2-hydroxypropyl)
They are aniline, N, N, bis(2-hydroxyethyl)aniline, and ethylenediamine.

The blend ratio of these crosslinking agents and liquid rubber is 10
50 parts by weight or less, preferably 1 to 20 parts by weight based on 0 parts by weight
It is best to use within the weight range.

As the anti-aging agent, general ultraviolet mold absorbers and antioxidants can be used. Examples include benzotriazoles, benzophenones, salicyl acid tlj conductors, monophenols, naphthylamines, phenylenediamines, and polyphenols.

Carbamates, wax fabrics, etc. can be used, and these may be used alone or in combination with 211fI4 or more.

The blending ratio of these anti-aging agents and liquid rubber is liquid rubber 1
20 parts by weight or less per part of 001r, preferably #i1
It is preferable to use O in a range of 1 to 10 parts by weight.

Process oils are aromatic and naphthenic.

Paraffin-based lubricating oil, such as spindle oil, can be used, as well as a lubricant such as DOP.

Pond plants can be used, and these may be used alone or in combination of two or more.

The blend ratio of these process oils and liquid rubber is preferably 100 parts by weight or less, preferably 10 to 50 parts by weight, based on 100 parts by weight of liquid rubber.

As a urethanization catalyst, a general urethanization catalyst is l#
can be used without restriction. Examples include amines and organotins #lI. These urethane-containing tFi
They may be used alone or in combination of 2m1111 or more.

As the blend polyol, all polyols for urethane that can be blended with liquid rubber can be used, and both polyester polyols and polyether polyols can be used.

Further, the number of functional groups, molecular weight, etc. may be arbitrary, but from the viewpoint of reactivity, those having a large number of primary OH values at the molecular ends are preferred.

As the colorant, both organic and inorganic pigments can be used. Further, flame retardants, antistatic agents, etc. can also be added depending on necessity.

Examples of #I include vertical hydrogen compounds (for example, n-butane, n-pentane, n-hexane, gasoline).

petroleum spirit, cyclohexane, etc.), aromatic hydrocarbon compounds (e.g. benzene, toluene, xylene, ethylbenzene, etc.), halogenated hydrocarbon compounds (e.g. methyl chloride, methylene chloride, etc.).

Chloroform, tetrachloride, ethyl chloride, ethylene chloride, trichloroethane, tetrachloroethane.

trichlorethylene, tetrachlorethylene, trichlormonofluoromethane, dichlorodifluoromethane, etc.)
, halogenated aromatic hydrocarbon compounds (e.g. chlorobenzene, chlorotoluene, brombenzene, etc.), ether compounds (e.g. ethyl ether, inglovir ether, dioxane, tetrahydrone), ketone compounds (e.g. acetone, methyl acetate/ , methyl ethyl ketone, methyl imbutyl ketone, cyclohequinanone group), ester compounds & (for example, ethyl acetate, methyl acetate, inbutyl acetate, ethyl propionate, gropionate) can be used.

In addition, water and alcohol compounds can also be used.

These solvents are added to the liquid rubber compound as necessary to adjust the viscosity of the rubber compound and facilitate handling and mixing with incyanate. The amount of the solvent added is preferably 100 parts by weight or less, preferably 1 to 10 parts by weight, per 100 parts by weight of the liquid rubber.

When mixing the various liquid rubber additive components as mentioned above,
i. It can be sufficiently dispersed using a general rubber paste stirrer or the like, and if necessary, it is preferable to use a five-roll mill or the like for uniform dispersion.

Examples of the polyisocyanate in the present invention include hexamethylene diisocyanate, phenyl diisocyanate, toluene diisocyanate, diisocyanate, and modified products and derivatives thereof.

All general polyinsyanates for urethane such as crude products can be used, and the c, Nco, 10H ratio may be arbitrary, but N
C! 010H=100-110/100 (D range concave is preferable.

As the base material in the present invention, any base material commonly used for rubberized fabrics can be used. - To give an example,
These include polyamide, polyester, polyurethane, polypropylene, vinylon, and fabrics with an li of 1.31.

Next, a manufacturing method for manufacturing the rubberized fabric of the present invention will be described.

First, the above-mentioned liquid rubber and polyisocyanate are placed in separate tanks, and each tank is continuously led to a mixing and discharging machine. Dispense once and apply evenly with a doctor knife, etc. In this case, unless the reaction product easily seeps out to the base material layer side due to the s#A of the base material, or the lAI& of the base material is extremely coarse or thin, this & Before the fabric process, in order to prevent the melted rubber compound from seeping into the base material 1 in the conventional comb-drawn fabric manufacturing process, and in the calendar topping method, a thin layer of rubber separated from the calender and the base material are mixed. The process of subbing the rubber @, which is essential for adhesion, can be completely omitted.

Furthermore, the adhesive strength between the base material and the reaction product is superior to that of conventional rubberized fabrics because it is crosslinked through a urethanization reaction.

In this way, the rubberized fabric coated directly on the base material is introduced into a crosslinking furnace to carry out crosslinking. Alternatively, liquid rubber and polyic anate are mixed and stirred using a mixing and dispensing machine, and then discharged onto silver paper, and evenly coated with a doctor knife, etc., and semi-crosslinked in a first crosslinking furnace, and then mixed with a base material. The coated layer on the IImW paper is pasted together, pressed using a pressure roll or the like, and crosslinked in a crosslinking furnace No. 1 and No. 20. The temperature condition in the crosslinking furnace may be room temperature or may be raised to 120° C.am. Thereafter, the rubberized cloth is peeled from the release paper to complete the transfer.

Either spray directly onto the substrate using a mixing and dispensing machine, or -
A product is produced by laminating a reaction product of liquid rubber and polyisocyanate on a base material by applying it to children's paper and transferring it to the base material. At this point, powder may be further sprinkled on the surface of the reaction product and brushed.The powder used here is intended to impart slipperiness to the surface and prevent stickiness. ! All of the commonly used formulas can be used. Examples include Merck, Silica,
Examples include ebonite powder, zinc stearate, zinc white, magnesium carbonate, calcium carbonate, clay, and aluminum oxide.

By applying the appetizer, the surface is made slippery,
Rubberized fabric has good adhesive and texture.

In addition, reactive powders such as wheat, starch, potato starch, and cellulose that have hydroxyl groups that react with polyicanate can be used. Excellent sex.

In addition, the reaction product of the rubberized fabric obtained by the method for producing a rubberized fabric of the present invention was again coated on the unlayered surface of the evaporated surface using the method described above. It is also possible to obtain a rubberized fabric cone product by laminating fL products.

The rubberized fabric of the present invention forms a rubber layer through the reaction of liquid rubber and polyisocyanate, so it can be used for rubber boats, raincoats, etc.
The physical properties of water spraying as a material for mats, etc., such as flexibility,
The water pressure resistance, weather resistance, tensile strength, and tensile strength are almost the same as conventional drawn fabrics.

The rubber-coated fabric of the present invention uses liquid rubber and polyisocyanate, so it can always be applied stably without changing over time or thickening like a rubber compound dissolved in a solvent. In addition, there will be no problems with quality.

Rubberized fabric I of the present invention! Since there is a sticky reaction product in i*m, conventional rubber-coated fabrics using solid rubber have good powder O* movement, less falling off of powder over time, and less slipperiness. It is something that lasts.

In addition, the rubber-coated fabric of the present invention is coated with reactive powder 11J as powder.
If the crosslinking of the reaction product is in a semi-crosslinked state, the reactive dusting powder will be strong due to the tackiness of the reaction product and the reaction between the reactive substance and the reactive dusting powder. Since it is bonded to the reactive powder, the adhesiveness and lubricity of the reactive powder are extremely long-lasting.

Compared to the conventional manufacturing method of rubber-coated cloth using the calender topping method, the manufacturing method for manufacturing rubber-coated cloth pipes of this company has a method called Martian scissors called calendar [even if it is not used].
The mixing discharge ifk is good, and depending on the casing base material, the process of lowering the rubber #A tube can be omitted, so there is no need for a huge investment in equipment, and only a small amount of equipment installation space is required, which shortens the process etc. The number of workers can also be reduced.

The method for producing rubberized cloth of the present invention is as follows:
It does not require vulcanization in a high-temperature atmosphere of 0°C or higher, and since it is a urethanization reaction, it can be cured at temperatures as low as 120°C even if the room temperature rises.
It also has advantages in terms of o and energy.

Sara K has the advantages of low-temperature crosslinking, such as less deterioration and shrinkage of the drawn fabric due to high-temperature vulcanization, and less volatilization of low-boiling components (for example, process oil) from the rubber compound.
The curling property of rubber-covered fabric (M) (the tendency of the fabric to curl due to rubber III) is extremely low, and rubber-covered fabric O&
It is even more advantageous in terms of secondary processing such as manufacturing and adhesion.

In addition, the method for manufacturing rubberized cloth of the present invention requires almost no bath additives compared to the conventional method of manufacturing rubberized cloth tubes by dissolving type 1 rubber in a solvent and applying it to a base material. Since it does not contain solvents, there is no need to apply it in several thin layers to prevent bubble formation, and even thick rubber-coated cloth can be produced with one application, making it easy to use in the resuscitation process. There is no need to repeat it. In addition, on the solvent side, the aging agent used in the solution is an indispensable material because it is volatilized to form a rubber layer, but the rubber coating of the present invention is
In HTV manufacturing, since one liquid rubber compound containing almost no bath agent is used, there is no waste such as volatilization of a large amount of O solvent, which is preferable from the point of view of resource saving.

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

Example 1 (Blend content) Liquid polybutadiene rubber (POIJBD R-45HT
(manufactured by ARCO) 100 parts by weight filler (aluminum hydroxide) 1so
Cross-linking agent (N, N-bis(2-hydroxyglobil)aniline) 51 Aging agent (BHT)
1 z process oil (DOP)
5 #Coloring agent (titanium oxide) 1
0 I urethanation catalyst (dibutyltin dilaurate)
α011 The above formulation was mixed with a stirrer, stirred uniformly, and poured into a tank of $1.

Next, polyisocyanate [Millionate MTL.

Fir manufactured by Nippon Polyurethane Co., Ltd. is put into the second tank.

Lead from each tank to the mixing discharge machine, N co / OH
The two liquids, whose index was adjusted to 105, were thoroughly mixed and stirred, and then tied with 210 denier nylon thread, each having a width of 40 mm.
Discharge onto nylon taffeta book and apply continuously at a basis weight of 300t/wl.

Next, heat crosslinking was performed at 80° C. for 4 minutes in a crosslinking furnace to obtain a rubberized cloth that was sprinkled with wheat starch, brushed, and wound up.

Example 2 Using the same formulation and mixing/discharging ratio as in Example 1, continuous coating was performed on silicone release paper at a basis weight of 1009/-.

Next, in the first crosslinking furnace, a heating rack of 4iI at 100°C for 2 minutes was applied.
After doing this to create a semi-crosslinked state, it was bonded to nylon taffeta with 100 strands of nylon thread of 70 denier and 90 strands of nylon taffeta in the width, and was crimped with a crimping roll.

Next, heating crosslinking was carried out at 100° C. for 2 minutes in a 20th crosslinking furnace, and wheat starch was sprinkled while releasing silicone release paper III, brushing was performed, and the cloth was wound up to obtain a rubberized cloth.

A nylon tack similar to that in Example 2 was prepared 7, and chloroprene rubber III (solid content 50X) was placed on the tack.

Solvent Doluol) was applied at a basis weight of 40 f/d and immediately dried at 100°C for 1 minute.

Next, the same liquid rubber compound and polyisocyanate as in Example 1 were completely mixed and discharged onto the nylon tack after subtraction drying at a mixing ratio of 100 t/m as in Example 1.
It was made into a continuous cloth with a basis weight of d, heat-crosslinked at 100° C. for 2 minutes in a crosslinking furnace, and after spraying wheat starch, it was brushed to form a rubberized cloth.

Ratio Soft Example 1 Center 11A Apply SBR-based -th undercoat @@t-5at/wto basis weight C on the same nylon tack as in Example 1, 1
After heating at 00°C for 1 minute, the film is wound up.

Next, it was divided into 1005'/m' basis weight using a calendar.8
B Undercoating R series rubber thin film and rubber needle lowering meeting 1 Lowering base material and [
After topping, wheat starch was sprinkled and brushed to obtain Ik cut #51, followed by O vulcanization at 150° C. for 5 minutes to obtain rubber coated fabric 1.

Comparative Example 2 Comparative Example 1 and ``-'' nylon tack and rubber undercoating glue were further applied under the conditions of KfFiJ, and the surface was coated with a mixed solvent of Toluay/D gasoline-171 weight ratio. SBR type homomorphic rubber melted, solid content 50XKI
The prepared coating material was coated with a basis weight of t1o or r/s/, heated at 100°C for 2 minutes, rolled up, and again applied to the surface of the rubber layer with a basis weight of t80f/j.
After heating at 0° C. for 2 minutes, wheat starch was sprinkled on the cloth, brushed and wound up, and vulcanization was completed at 150° C. for 5 minutes to obtain rubberized fabric 1.

At the time of the visit, due to the thickening of the applied material over time, the preparation time was 30%.
I went minute by minute.

The monovalent results for each applied fabric are shown.

t Smoothness test: Smooth surface width 20 m, length 5
0 stroke, 10. on an aluminum plate with thickness S-. Place the corner cloth with the rubber side facing down. Fix the lengthwise end of the aluminum sheet, gradually lift the other end upwards, and record the sound at the corner when the cloth starts to slide.

The more angles there are, the worse the angle is.

2 Smoothness O Retention A 10α square drawn fabric is washed with water in a washing machine for 50 minutes, and after drying, it is evaluated in the same manner as the slickness test.

5. Curl property 30C11 corner cloth 50℃ x 80X
After being left in a humid atmosphere for 24 hours, the curling property of the drawn fabric was visually confirmed.

Reviewer: The edges of the sample are slightly curled.

B Half of the sample 11 degrees curl C The sample is completely curled into a roll. The above results? It is compiled and displayed in Table 1.

As is clear from Table 1, the rubber-coated fabrics of the examples were subjected to a lubricity test to show the adhesion of powder, a lubricity test after washing to show the sustainability of the adhesion of powder, and a lubricity test under high humidity. It can be seen that the curling properties of the original fabric are superior to those of the comparative example, which is a conventional product.

patent applicant

Claims (1)

[Claims] 1. At least one side of the base material may be laminated with a reaction product of Kg-like rubber and polyinocyanate. 1. Rubberized fabric 2. jj reaction product O1! Claims wAI where powder is sprinkled on the surface
The rubberized fabric 5 according to claim 11 is obtained by blending a water-absorbing agent with a rubber-like rubber.The rubber-coated fabric 4 according to claims 1 and 2 is obtained by blending a reaction regulator with a rubber-like rubber. The rubber coated cloth Sg-like rubber and polyinocyanate described in the above section are continuously mixed and stirred using a mixing and discharging machine, and the mixture is discharged directly onto the base material, or the base material KI [high transfer Manufacturing method of rubberized cloth using tube 41 mold