JPS6017176A - Adhesive treatment of polyester fiber material - 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 method for treating a polyester fiber material for rubber reinforcement with an adhesive that has improved adhesion to rubber.

Polyester fiber materials generally have excellent properties such as tensile strength and dimensional stability, and are suitable as rubber reinforcing materials for automobile tires, conveyor belts, belts, hoses, etc. However, since polyester fiber materials have poor adhesion to rubber, many proposals have been made to improve the adhesion. For example, a method in which a polyester fiber material is treated with a first treatment bath containing a polyepoxide compound and an aromatic polyisocyanate compound, and then treated with a second treatment bath containing a mixture of resorcinol, formaldehyde and rubber latex, so-called RFL (particularly Publication No. 42-11482) is known. However, although fiber materials treated with this method exhibit relatively good adhesion to rubber, they have the drawbacks of becoming hard, making it difficult to bend during molding, and significantly reducing fatigue resistance. have Alternatively, a method (Japanese Patent Publication No. 42-9004 A method of treating a polyester fiber material with a first treatment bath containing a polyepoxide compound, a blocked polyincyanate compound and a rubber latex, and then treating it with a second treatment bath containing resorcinol, formaldehyde, rubber latex and an ethylene urea compound. (Tokuko Showa 5
No. 7-21587 is also known, but polyester fiber materials treated with these methods do not have the problem of hardening, but on the other hand, when the fiber material is peeled from the rubber composite molded product, the fiber material may be hardened. A problem arises in that the rubber adhesion rate is low and the adhesive force between the polyester fiber material and the rubber is reduced. Therefore, it has been extremely difficult to satisfy all of the requirements for adhesion to rubber, flexibility, and fatigue resistance for polyester fiber materials.

Therefore, the present inventors have conducted extensive studies with the aim of solving the above-mentioned drawbacks and establishing a method for obtaining a polyester fiber material that has sufficient adhesion between the polyester fiber material and rubber, is flexible, and has excellent fatigue resistance. A so-called two-bath method is used, which consists of a combination of a first treatment bath containing a polyepoxide compound, a comb latex, and a blocked polyisocyanate compound, and a second treatment bath containing a mixture of resorcinol, formaldehyde, rubber latex, and a blocked polyin 7-anate compound. The present invention has been achieved by discovering that the above object can be effectively achieved by mixing a specific amount of carbon blank into one or both of the above treatment baths when treating polyester fiber materials. did.

That is, the present invention combines a polyester fiber material with (Fl polyepoxide compound, (G) rubber latex and +I (
+ blocked polyisocyanate compound, followed by treatment with 1,1 fXl resorcin, (Y
) formaldehyde, +G) rubber latex and (
When treating with a second treatment bath containing a blocked polyester or a soocyanate compound, at least one of the treatment baths is treated with the total solid weight ((Fl) contained in the treatment bath.
+ (Gl + (Hl or (xi ten(y)++o
)+(H) 0.3 to 30 parts by weight of carbon blank is mixed in a processing bath.

The polyester fiber material used in the present invention refers to yarn, cord, or woven fabric made of aromatic ring-containing linear polyester fibers such as polyethylene terephthalate and (1) ethylene naphthalate. It goes without saying that the form of the polyester fiber material differs depending on its use, but the adhesive treatment of the present invention can be applied to any form.

The +F) bonoepoxide compound used in the first treatment bath of the present invention is a compound having two or more epoxy groups in one molecule, such as ethylene glycol, glycerol, sorbitol, pentaerythritol, polyethylene Reaction products of polyhydric alcohols such as glycols and halogen-containing epoxides, polyhydric phenols such as formaldehyde resins, resorcinol formaldehyde resins, and the above-mentioned epoxides containing halogens. It is possible to list reaction products with Preferably, a polyglycyl ether of a polyhydric alcohol obtained from a polyhydric alcohol and epichlorohydrin is used.

Examples of the Gl rubber latex used in the first treatment bath of the present invention include natural rubber latex, styrene-butadiene copolymer latex, vinylpyridine-styrene-tatadiene-polymer latex, and Nido 1 Norco.

Among these, (vinylpyridine/styrene-)oxyene/2-polymer latex exhibits excellent properties when used alone or in combination with other rubber latexes. fH) Blocked polyiso7anate compound used in the first treatment bath 1 of the present invention is an adduct of a polyincyanate compound and a blocking agent, and specifically, tolylene diisocyanate, metaphenylene diisocyanate, etc. Polyincyanate compounds such as iso/anate, diphenylmethane diisocyanate, hexamena diisocyanate, and triphenylmethane triincyanate, phenols such as phenol, cresol, and resorcinol, lactams such as caprolactam and valerolactum, acetoxime, cyclohexane oxytum, etc. oximes, t
- Addition compounds formed by widening tertiary alcohols such as butanol and t-pentanol and blocking agents such as ethyleneimine, preferably phenol-blocked compounds such as phenol-blocked products of diphenylmethane diisocyanate. of polyiso/anate compounds are used.

The first treatment bath of the present invention is an aqueous liquid containing the blocked polyisocyanate compound (Fl polyeboxide compound, (G) rubber latex, and iH); (The mixing ratio of (F) / (Fl + (1-11) is 10 to 80% by weight, especially 20 to 50% by weight, and (Fl +
(per +100 parts by weight (Gl) is suitably in the range of 50 to +000 parts by weight, especially 80 to 500 parts by weight. Outside this range, the rubber adhesion rate to the treated polyester fiber material is poor and the adhesion is poor. It is not preferable because the value of (F) + (G) in the first treatment bath decreases.
+ (The total solid concentration of Hl is 1 to 30% by weight, especially 5
~15% by weight is suitable. If the amount of the treatment agent attached to the polyester fiber material is too small in proportion to the degree of d, the adhesion of the polyester fiber material to rubber will decrease, and if it is too large, the polyester fiber material will become hard and its fatigue resistance will decrease.

The (X) resorcinol, (Yl formaldehyde and (Gl) rubber latex used in the second treatment bath of the present invention is usually prepared by first condensing the above (Xl and (Yl) in the presence of an alkali catalyst, then adding the above +G to this). The rubber latex (G) used here is the same as that explained in the first treatment bath.And ( The molar ratio (X)/(Y) of X) resorcinol and (Y) formaldehyde is O, Z~5, especially 0.5~2
The solid weight ratio of rubber latex and (X) resorcinol and (Y) formaldehyde is (x) + ty) j O0 parts by weight, fG) is 10
A range of 0 to 2000 parts by weight, particularly 600 to 1000 parts by weight, is suitable.

The Hl-blocked polyisocyanate compound used in the second treatment bath of the present invention overlaps with that described in the first treatment bath, but may be the same as or different from that used in the first treatment bath. As the fHl-blocked polyisocyanate compound used in the second treatment bath, phenol-blocked polyisocyanate compounds of diphenylmethane diisocyanate and ethyleneimine-blocked polyisocyanate compounds are particularly preferred.

The second treatment bath of the present invention is an aqueous liquid containing the above-mentioned (X) resorcinol/fY) formaldehyde/(Gl-f mulatex mixture (hereinafter abbreviated as R, FL) and (Hl blocked polyisocyanate compound). The ratio of RFL and (H) in the solid content is i to 100 parts by weight of RFL.
A suitable range for q) is 1 to 30 parts by weight, particularly 5 to 20 parts by weight. Here, iH1 force (outside the above composition range cannot expect much improvement in the adhesive strength of the treated fiber material to rubber. Also, Rpb+ (H
) has a solid content of 1 to 50% by weight, especially 5 to 2
0% by weight is suitable; outside this range, the adhesion of the treated fiber material to the rubber tends to decrease.

To prepare the second treatment bath, it is common to first ripen the RFL and then mix it with a (l-blocked polyisocyanate compound). It is also possible to add topolyisocyanate compounds.

Aging of RFL is usually carried out at 20 to 30°C for 24 hours or more.

A first treatment bath containing the above CF+Fl epoxide compound, (Gl rubber latex and (I(+) blocked polyisocyanate compound, and (X) resorcinol/(Y) formaldehyde/fil rubber latex mixture (RF L
) and (f(2) containing a blocked polyisocyanate compound) The adhesive properties of the treated polyester fibers to rubber have been improved to some extent, but this is still insufficient.

However, in the present invention (J6), it is an essential requirement that a specific amount of carbon blank be blended into either or both of the first treatment bath and the second treatment bath, thereby making it possible to reduce the thickness of the treated fiber material. The adhesion to is greatly improved.

However, the carbon blank used in the present invention is a carbon black commonly used in the rubber industry with an average particle size of 1 mμ to 500 mμ, such as SAF, 15AF+H.
AF, GPF, FT, MT.

Examples include EPClIllPc, FF, SRF, etc., and SA'F and HAF with an average particle size of about somμ or less.
, ISAF's black one is particularly preferably used.

It is preferable that these carbon blacks are made into an aqueous dispersion using an arbitrary dispersant and mixed into the first treatment bath and/or the second treatment bath.Additionally, the timing of adding the carbon black is also arbitrary. 2 treatment bath tone 1lii!
In this case, carbon black may be mixed with the aged RFL, and carbon blank and Zl blocked polyisocyanate may also be mixed with the aged RFL.

The blending amount of carbon black is determined by the total weight of solids contained in the first treatment bath and/or the second treatment bath ((Fl + (o
l + (H] or (X) + (Y) + (Gl
+ (Hl,) The appropriate range is 03 to 30 parts by weight, and 08 to 15 parts by weight per 100 parts by weight.
If the amount is less than 6M parts, the effect of improving the adhesion of the treated fiber material to rubber is insufficient, and if it exceeds 30 parts by weight, not only will the adhesion to rubber deteriorate, but the properties of the fiber material itself will be impaired. Therefore, it is undesirable.

Carbon black is added to either or both of the first treatment bath and the second treatment bath, but when it is added to only one of the baths, it has a particularly pronounced effect when added to the first treatment bath. can get.

To coat the polyester fiber material with the first treatment bath and the second treatment bath, the yarn is coated in the first treatment bath and the second treatment bath.
It can be contacted with a treatment bath and then formed into a cord or woven fabric, or it can be contacted with a first treatment bath and then formed into a cord or woven fabric, and then contacted with a second treatment bath.

Furthermore, the cord or woven fabric may be coated and then brought into contact with the first treatment bath and the second treatment bath sequentially. Preferably the last method is adopted. In the present invention, the term "treatment" includes any means for bringing the yarn, cord, or woven fabric into contact with the treatment bath, such as a method of immersing the fibers in a treatment bath r:i, or a method of applying a treatment liquid to the fibers. Examples include a method of spraying from a nozzle and a method of coating with a treatment liquid such as 10-color.

The amount of solid content deposited on the polyester fiber material is 0.1 to 7%, preferably 0.5 to 7% as a component of the first treatment bath.
It is preferable to control the content within the range of 3% by weight, and 0.1 to 10% by weight, preferably 05 to 50% by weight as a component of the second treatment bath. In order to control the amount of solid content deposited in the treatment bath on the polyester fiber material, means such as squeezing with a pressure roller, blowing off with air, and suction can be used.

In the present invention, after treating the polyester m fiber material in the first treatment bath, it is dried at a temperature of 80 to 150°C, and
It is desirable to carry out the heat treatment at a temperature of 260°C, preferably 200-240°C.

Then, after being treated with a second treatment bath, it is dried at a temperature of 60 to 150°C, and then dried at a temperature of 200 to 260°C, preferably 220 to 25°C.
The desired adhesive treatment is completed by heat treatment at a temperature of 0°C. If the heat treatment is too gentle, the adhesion between the polyester material and the rubber will be insufficient; on the other hand, if the heat treatment is too harsh, the polyester fiber material will melt or fuse, resulting in a further significant decrease in strength, making it unsuitable for practical use. This is not preferable because you will not be able to obtain any benefits.

The polyester fiber material treated in this way has general properties such as excellent tensile strength and dimensional stability for rubber reinforcement, and is particularly flexible, has low bending hardness, and has good moldability. It has excellent fatigue resistance, high adhesive strength after vulcanization by being embedded in compounded rubber, and extremely high adhesion rate of rubber to polyester fiber materials.

The reason why a treated polyester fiber material that is flexible and has an extremely high rubber adhesion rate can be obtained by the present invention is not clear, but the reason can be estimated from the characteristics of the carbon blank as follows. That is, the functional groups present in the carbon black particle surface layer, such as carboxyl groups, carbonyl groups, quinone groups, and hydroxyl groups, are present in the polyepoxide compound, blocked polyisocyanate compound, resorcinol formaldehyde condensate, and rubber latex, which are components of the TOCA treatment solution. The structural feature of the carbon black particles, such as their large surface area, increases the number of contact points with each compounded component in the treatment liquid described in 011, thereby increasing the cohesive force within the adhesive layer. results that improve
It is presumed that a strong adhesive bond can be obtained between the polyester m-fiber material and the polyester m-fiber material.

EXAMPLES The present invention will now be explained in more detail with reference to Examples. In the examples, the inter-ply peel force indicates the adhesive strength between the polyester fiber material and rubber, and a treated cord is inserted between two plies of treated cord so as to form a 90 degree angle, and a cross-ply (cord Density 30 end/25g1+)
The force required to peel the plies at a tensile speed of 5.0 a/min after embedding them in carcass compound rubber for automobile tires and press-vulcanizing them at 150°C for 50 minutes was expressed in kg/20 m. It is something. Rubber adhesion rate is also a measure of the adhesion of rubber to polyester fiber materials.
Observe the separated cord with the naked eye and rate the percentage of rubber adhering to the cord surface in five stages [A (rubber adhesion rate 81 to 1).
00%, B (rubber adhesion rate 61-80%), C (rubber adhesion rate 41-60%), D (rubber adhesion rate 21-4096)
, E (rubber adhesion rate of 20% or less)] and are designated by symbols. The bending hardness of the cord is measured using the Gurley method, and the higher the measured value, the harder it is.

Furthermore, the strength retention rate is a measure of fatigue resistance.
This is the strength remaining after 48 hours (1705 rpm) of a cord subjected to repeated fatigue at a setting of 5% elongation and 10% compression between rotating disks using a Ricci disc tester, expressed as a percentage.

Example (17.5 g of Fl glycerol polygrindyl ether (manufactured by Nagashio Sangyo Co., Ltd., Bunacol EX-314) and 7 g of distilled water
Add 29.0 E and homogeneously dissolve it, and further add (0) vinylpyridine-styrene-phytadiene terpolymer latex (manufactured by Nippon Seon Co., Ltd., 2518F) to this aqueous solution.
! S, 411.5% emulsion) 123,5 g16 J:
2 of H (R1 phenol block product of diphenylmethane diisocyanate (manufactured by DuPont), Irene MP)
Add 1,600 g of 5% aqueous dispersion and disperse it evenly.
A treatment bath was prepared.

The solid content of this first treatment bath ((F) + (Gl + (
Hl) concentration was 10%, (Fl/(Gl/(River weight ratio) was 175/32.5150.

Meanwhile, distilled water 189.2 g, resorcinol 10.9 g
, .

An initial condensate was prepared from 161 g of 37% formaldehyde and 3'2.4 g of a 1% caustic soda aqueous solution, and this condensate was converted into vinylpyridine/styrene/]tatadiene terpolymer Latexox, manufactured by Zeon Co., Ltd., 2518FS, 40
．． 1846g of 5% emulsified feces, styrene-butane-ene copolymer latex (manufactured by Nippon Zeon Co., Ltd., LX-112,
4α5% emulsion) 61.5g, 28% ammonia water 11
．． 3 g and 494 g of distilled water for ripening, and then added to this (F(+25% aqueous dispersion of phenol-blocked product of diphenylmethane diisocyanate (manufactured by DuPont, Nohain MP) 4).
a A second treatment bath was prepared by adding Og. Solid content of this second treatment bath [(X) 10 (Yl + (G) + (for)]
The concentration is 12.3% by weight, RFL (ix) + (Y
)+1Gl) was contained at a ratio of 10 parts by weight (R) per 10 parts by weight.

600 g of distilled water, 1% caustic soda solution 1
25 g,') Sodium geninsulfonate (dispersant) 25
gf6 and carbon black (manufactured by Asahi Carbon Co., Ltd., HAF
) 250 g was dispersed in a ball mill for 48 hours to obtain a carbon black dispersion, and this dispersion was added to the first treatment bath and/or the second treatment bath so that the amount of carbon black added was in the ratio shown in Table 1. It was blended into.

+500D/2 strands combined, top twist 40 times/10α, bottom twist 40
Contributor processing machine for coats made of polyester fibers (C, A).

(manufactured by RenoSolar) in the first treatment bath, dried at 100°C for 150 seconds, and then heated to 260°C for 60 seconds.
Heat treatment was performed for 0 seconds. The cord was then immersed in the second treatment bath, dried at 100°C for 150 seconds, and then heat treated at 240°C for 60 seconds. The polyester cord obtained by such e-treatment has a solid content of 2.7% by weight in the first treatment bath.
A solid content of 1.3 weight ♂ from the second execution bath was attached. Regarding the obtained treatment code, inter-ply peel force, rubber adhesion rate,
Cord strength, cord bending hardness, and strength retention after fatigue were measured. The results are also shown in Table 1.

As is clear from the results in Table 1, the method of the present invention (51
According to ~B), a polyester fiber (cord) having excellent adhesion to rubber, flexibility, and good fatigue resistance can be obtained.

On the other hand, when carbon black is not added (Aq), when the amount added is small (sections 10 to 12), and when it is too large (Aq),
3.14) all have poor adhesion to rubber, and when the rubber latex is removed from the first treatment bath (A 15 ), the hardness of the fibers increases and the fatigue resistance becomes extremely poor.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] After treating the polyester fiber material with a first treatment bath containing (F) a polyepoxide compound, (G) rubber latex and (H) a blocked polyinsyanate compound, it is subsequently treated with (Xl resorcinol, (yL formaldehyde,
G) Rubber latex and (Hl blocked polyiso/
When performing treatment with the second treatment bath containing an anate compound, at least one of the treatment baths has a total weight of solids contained in the treatment bath ((Fl + (o) + (H)
or α) + (Y) + (G) + (Hj)
An adhesive treatment method for polyester fiber material characterized by using a treatment bath in which 0.6 to 60 parts by weight of carbon blank is mixed per 100 parts by weight.