JPH08269421A - Adhesive composition - Google Patents

Abstract

PURPOSE: To obtain an adhesive composition for bonding a heat-resistant polyester fiber by mixing a specified cresol/aminophenol/formaldehyde cocondensation resin with a specified terpolymer latex and a resorcinol/formaldehyde precondensate. CONSTITUTION: This composition comprises an m-cresol/m-aminophenol/ formaldehyde cocondensate (A) (the ratio between the monomers is 1/0.5 to 1/2; and the molecular weight distribution is such that the areal ratio of a component composed of at least four bonded benzene rings is 35-65%, and the areal ratio of a monomer component is 10% or below, a terpolymer latex (B) obtained by polymerizing a mixture comprising 5-15wt.% vinylpyridine, 40-70wt.% styrene and 15-55wt.% butadiene and then polymerizing a mixture comprising 5-20wt.% vinylpyridine, 10-40wt.% styrene and 45-75wt.% butadiene (the ratio between the weights of the polymers obtained by the former and latter polymerizations is 50/50 to 80/20) and a resorcinol/formaldehyde precondensate and satisfies the equations (wherein (A), (B) and (C) are the weights (in terms of the weight of nonvolatiles) of the respective components).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an adhesive composition,
In particular, it relates to an adhesive composition suitable for adhering polyester fiber and rubber.

[0002]

2. Description of the Related Art Polyester fiber material, which is a linear polymer having an ester bond in the main chain, represented by polyethylene terephthalate, has a high initial modulus of elasticity and high heat resistance in general-purpose polymer materials. Since it has dimensional stability and is excellent in cost, it is in the form of filament yarn, cord, cable, cord fabric, canvas, etc.
It is extremely useful as a reinforcing material for rubber articles such as tires, belts, air springs and rubber hoses.

By the way, when the fiber material is used as a reinforcing material for a rubber article, it is necessary to bond the fiber material and the rubber. In addition, when bonding fiber materials such as nylon and rayon to rubber, RFL liquid (resorcin.
An adhesive consisting of formaldehyde precondensate and rubber latex can be preferably used. However, since the polyester fiber is structurally dense and has few functional groups, almost no adhesion can be obtained with the RFL liquid.

Therefore, in order to obtain an adhesive effect with the RFL solution, alkali amine treatment is performed to increase the number of active groups such as --OH, --COOH, and --NH _{2 on} the polyester surface, and to obtain isocyanate compounds and epoxy compounds. Depending on the compound, a compound having a hydrogen-bonding ability or a functional group capable of primary bonding was introduced on the surface of the polyester, but in the former method, the strength of the polyester fiber deteriorates, and in the latter method. However, there were the following inconveniences.

That is, (1) an isocyanate compound and an epoxy compound are highly reactive and react with water, which is a solvent of the RFL solution, and the resorcin / formaldehyde initial condensate in RFL, so that not only the adhesive property is impaired, Since it is extremely difficult to make a one-liquid adhesive solution, the bonding process must be performed in two stages, which requires extra equipment and steps, which deteriorates workability and reduces costs. This is not preferable from the viewpoint of resource saving and energy saving. (2) Isocyanate compounds and epoxy compounds are scattered in the air during the bonding process, and smoke and vapor are generated during the heat treatment, deteriorating the working environment. (3) The polyester fiber material treated with an isocyanate compound or an epoxy compound is cured and becomes difficult to handle in manufacturing; (4) Further A rubber article reinforced with a polyester fiber that has been subjected to this treatment has a markedly reduced product life when it is used under high temperature and high strain due to rapid adhesive deterioration and strength deterioration of the fiber material. ;

The reason for this is that the isocyanate compound and the epoxy compound are primary bonded on the surface of the polyester fiber to form a kind of graft polymer on the surface. Adhesive failure of this part is easily caused by aminolysis due to the vulcanizing agent residue inside, and under high strain, it is weak against mechanical input due to a large rigidity difference between the inside of the polyester and the surface. Can be mentioned. This is also because, for tires and the like, which are becoming lighter from the viewpoint of energy saving, it is required to improve stability against thermal input / mechanical input / improvement in fracture life more than ever before. It is not preferable to use an isocyanate compound or an epoxy compound for treating the polyester fiber material.

In addition, in order to eliminate the inconvenience of the two-part form of isocyanate compounds and epoxy compounds,
Although a reaction product of p-chlorophenol and formaldehyde or a reaction product of resorcinol and triallyl cyanurate, which can be adhesively processed in a one-liquid form, has been proposed, these have insufficient adhesion performance. In addition, it has the drawback of causing adhesion deterioration and fiber strength deterioration during continuous use under high temperature and high strain.

In order to solve the above various inconveniences, the present applicant has already found that the strength deterioration of the polyester fiber material is small,
It is a one-liquid type with high adhesion performance, no toxicity or environmental pollution,
M-cresol and m-aminophenol are formaldehyde as an adhesive that does not harden the fiber material, has good workability, and has little adhesive deterioration and fiber strength deterioration during continuous use under high temperature and high strain. An adhesive composition containing a solution or dispersion of a resin obtained by co-condensation with a rubber latex or a mixed solution of a rubber latex and a resorcin-formaldehyde precondensate has been proposed (Japanese Patent Laid-Open No. HEI 3).
(See JP-A-121181).

However, in recent years, the performance of tires has been required to be improved, and in order to improve productivity, polyester fiber materials are processed from the process of processing to the point of use, such as vulcanization at a higher temperature than ever before. Thermal input is getting severer. Therefore, in reality, it is desired to develop an adhesive composition having heat resistance higher than that of the above-mentioned adhesive composition.

[0010]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an adhesive composition having the above-mentioned properties further improved, particularly an adhesive composition for bonding polyester fibers.

[0011]

In order to achieve the above object, the present inventors have made an adhesive containing a resin or the like obtained by co-condensing the above-mentioned m-cresol and m-aminophenol with formaldehyde as an adhesive component. As a result of various studies on the composition, a novel adhesive composition satisfying the above requirements has been developed.

The composition of the adhesive composition of the present invention is as follows. (1) (a) The co-condensation molar ratio determined from the proton intensity ratio of 1 H-NMR is 1: 0.5 to 1: 2, and the molecular weight distribution determined by gel permeation chromatography (GPC) is benzene. The area ratio obtained by the component in which four or more rings are connected is in the range of 35% to 65%, and the area ratio obtained by the monomer component is 10%.
A co-condensation resin of m-cresol and m-aminophenol, which is the following, and which is via formaldehyde, (b)
Vinyl pyridine content 5 to 15% by weight, styrene content 40 to 70% by weight, and butadiene content 15 to 55
After polymerizing the first monomer mixture, which is composed by weight percent,
Subsequently, a second monomer mixture having a vinylpyridine content of 5 to 20% by weight, a styrene content of 10 to 40% by weight, and a butadiene content of 45 to 75% by weight is polymerized to form a first monomer. Vinylpyridine having a polymer having a different composition ratio in the same particle, wherein the weight ratio of the first polymer obtained by the mixture and the second polymer obtained by the second monomer mixture is 50/50 to 80/20. -Styrene-butadiene terpolymer latex, and (c) resorcin-formaldehyde precondensate, containing the following 2
Formula (A) / {(B) + (C)} = 10/100 to 125 /
100 (C) / (B) = 2.5 / 100 to 25/100 (In the formula, A represents the solid content weight of the co-condensed resin, and B represents the solid content weight of the terpolymer latex. , C represents the solid content weight of the above-mentioned resorcinol-formaldehyde precondensate).

(2) (a) 0.5-2 mol of formaldehyde is added to 1 mol of m-cresol, and m-cresol is resolized at 20-100 ° C. in the presence of an alkali catalyst; ) After adding 0.5 to 3 mol of m-aminophenol to the reaction mixture and novolacing at 70 to 130 ° C; (c) Furthermore, a constant temperature range of 135 to 185 ° C under an inert gas atmosphere. A co-condensation resin obtained by: (d) heat-treating at a temperature of 130 to 220 ° C. under a reduced pressure of 5 torr or less; To do.

The present invention will be described in more detail. In the present invention, the co-condensate of m-cresol and m-aminophenol linked by formaldehyde is H-NMR.
M-cresol and m-cresol determined from the proton intensity ratio of
The co-condensation molar ratio of aminophenol is 1: 0.5 to 1:
It is necessary to be in the range of 2, but when the cocondensation ratio deviates from the above range, the binding force to the polyester fiber, particularly the diffusibility is lowered, and the reinforcing property to the rubber latex and the reinforcing aid of the rubber latex, RF It is not preferable because the reactivity with the resin decreases.

H-NMR was used to determine the co-condensation molar ratio.
Is calculated from the intensity ratio of the proton of the phenyl group or methyl group of m-cresol and the proton of the amino group of m-aminophenol.

Regarding the number of benzene rings of m-cresol and m-aminophenol of the co-condensed resin in the present invention, which are linked by a methylene group, the molecular weight distribution measured by GPC shows that the number of benzene rings is 4 (4 cores). Body) The area ratio obtained by the above connected components is 35% to 65
It is preferably in the range of%. If this area ratio exceeds 65%, the diffusibility and bond strength with respect to the polyester fiber will decrease, and if it is less than 35%, it will be reinforced to rubber latex or RF which is a reinforcement aid for rubber latex. The reactivity with the resin is lowered, and the adhesive force is lowered in any case.

Similarly, in the molecular weight distribution measured by GPC, the area ratio obtained by the monomer components is 10
% Or less is preferable. If this area ratio exceeds 10%, the adhesive strength will decrease, and the strength of the adhesive-treated fiber material will also decrease.

The number of nuclear bodies referred to in the present invention is determined by the following method using a GPC measuring instrument [trade name: HLC8020, manufactured by Tosoh Corporation]. 10 mg of sample (co-condensation resin) was added to THF10
ml was added and dissolved, and THF was used as a mobile phase, and the column 10
00HX and 2000HX are used by connecting them in series. Four
At an atmosphere temperature of 0 ° C. and a flow rate of 1 ml / min, the molecular weight pattern of the distillate is measured with an RI detector. The amount of each nuclide is determined by the following procedure from the GPC chart illustrated in FIG.

(A) The several peaks of the obtained GPC waveform are analyzed from the low molecular weight side to monomer M, dinuclear D, trinuclear T, 4
Nucleus Q, 5 nuclei or more P. (A) The lower ends of the waveform are connected, and this is used as the baseline (a). (C) A perpendicular line (b) is drawn from the valley of the waveform showing each molecular weight to the baseline. This is the boundary between adjacent nuclei with different molecular weights. (D) The area of the chart surrounded by one waveform showing each nucleolus and two perpendicular lines (b) and a baseline (a) partitioning the same is the entire area (enclosed by the GPC waveform on the baseline. It was expressed as a percentage with respect to the total area), and this was used as the content of each nucleus.

When co-condensing m-cresol and m-aminophenol with formaldehyde, heat treatment is performed in an inert gas atmosphere at a constant temperature in the temperature range of 135 to 185 ° C. for a fixed time in the time range of 30 to 180 minutes. If it is not carried out, even if a heat treatment is carried out at a temperature of 130 to 220 ° C. under a reduced pressure of 5 torr or less, preferably 2 torr or less, the monomer content in the final product becomes high, which is not preferable. When the extraction with a solvent such as
The ratio of nuclei or more is too high, which is not preferable.

An example of the method for producing the co-condensed resin in the present invention will be shown. A Kolben reactor equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel was charged with 1 mol of m-cresol, water (about 100 g) and 0.5 wt% of an alkali catalyst with respect to m-cresol, and 20- Heat to 100 ° C, 37%
0.5-2 mol (preferably 1.0-1.5 mol) of formalin aqueous solution is added dropwise to m-cresol over 0 to 1 hour. Thereafter, the first-stage resolization reaction is carried out at the above temperature for 0.5 to 8 hours.

M-Cresol 1 was added to this first-stage reaction mixture.
After adding 0.5 to 3 mol of m-aminophenol to the mol, the mixture is stirred at 70 to 130 ° C. for 10 minutes to 4 hours to react. At the same time, it is dehydrated and desolvated.

Next, after the temperature is raised to a constant temperature within the temperature range of 135 to 185 ° C., heat treatment is performed for a fixed time within the range of 20 to 180 minutes in an atmosphere of an inert gas (for example, nitrogen). The reaction monomer is converted into novolac.

Thereafter, if necessary, the mixture is heated to 130 to 220 ° C. under a reduced pressure of 40 torr or less, and the remaining water and solvent are distilled off over 30 minutes to 4 hours to complete the reaction in the second stage, A co-condensation resin of

Further, since the unreacted monomer affects the adhesiveness, when the content of the monomer in the co-condensation resin exceeds 15%, the temperature of 130 to 220 ° C. under reduced pressure of 5 torr or less, preferably 2 torr or less. 20 minutes to 1 hour,
Distill.

Regarding the resolization reaction, the reaction solvent is Na
Any metal hydroxide such as OH or an alkali such as an organic amine may be used, and Ca (OH) ₂ is preferably used. The amount used can be 0.01 to 3.0% by weight with respect to m-cresol, and is preferably 0.1.
5% by weight can be used. The reason for this is that if it is less than 0.01%, the reaction is slow, and if it exceeds 3.0%, the reaction becomes very fast, or on the other hand, it remains during use and adversely affects the adhesiveness, which is not preferable. .

The amount of formalin (37%) used relative to 1.0 mol of m-cresol can be 0.5 to 2 mol (formaldehyde), and preferably 1.2 to 1.5 mol. The reason for this is that if the amount is less than 0.5 mol, the monomer of m-cresol remains, resulting in poor yield.
On the other hand, if the amount exceeds 2.0 moles, m-cresol has a high molecular weight, and in some cases gels, which is not preferable.

The first stage reaction is generally carried out at a reaction temperature of 20.
The reaction is carried out at a temperature of up to 100 ° C., and the reason is that if it is lower than 20 ° C., resolization does not proceed, while if it exceeds 100 ° C., only m-cresol has a high molecular weight, which is not preferable. This is because the reaction time of the first step is generally 0.5 to 8 hours, and if it is less than 0.5 hours, the resolization does not proceed, and if it exceeds 8 hours, m-cresol has a high molecular weight. .

Regarding the reaction in the second stage, the method of adding m-aminophenol may be as it is because m-aminophenol is powder, or alcohol,
It may be dissolved in an organic solvent such as ether or water and added. In addition, in this reaction, oxalic acid, p
-Organic acid such as toluene sulfonic acid, HCl, H ₂ SO ₄
You may use inorganic acid, such as. The amount of m-aminophenol based on m-cresol can be 0.5 to 3 mol per 1 mol of m-cresol. The reason for this is 0.5
When it is less than the molar amount, the co-condensation resin has a high molecular weight, and
This is because if it exceeds 3.0 mol, the molecular weight is lowered and a large amount of the monomer remains, which is not preferable.

The reaction temperature in the second stage is preferably 70 ° C to 130 ° C, and the upper limit temperature is limited by the boiling point of the reaction solvent. The reaction time is preferably 10 minutes to 4 hours, especially 4 minutes.
If the time is exceeded, the cocondensation resin will have a high molecular weight, which is not preferable. After completion of the reaction, the temperature is raised to a constant temperature in the range of 135 to 185 ° C., and then heat treatment is performed in the atmosphere of an inert gas (for example, nitrogen) for a fixed time in the range of 20 to 180 minutes.

In the present invention, acidic, neutral or alkaline water or an organic solvent such as acetone or alcohol can be used as the solvent of the solution or dispersion of the co-condensed resin, but the adhesive composition of the present invention In this case, since it is mixed with the rubber latex, it is preferable to use alkaline or neutral water. Here, alkaline water is sodium hydroxide, lithium hydroxide, potassium hydroxide,
It is obtained by dissolving anmonium hydroxide or an organic amine such as monomethylamine in water. It is also possible to use any anionic surfactant dispersed in neutral water by a ball mill or a sand mill for use. In this case, in order to effectively develop the adhesive force, it is necessary to reduce the amount of the surfactant so that the dispersed state does not deteriorate.

Next, the contribution of the latex in the adhesive composition to the adhesion is as follows. The reason why the composition ratio of the first polymer and the second polymer constituting the vinyl pyridine-styrene-butadiene terpolymer particles in the latex is different is as follows. That is, the butadiene component that gives a double bond in the particles mainly undergoes a crosslinking reaction due to a crosslinking agent that migrates and diffuses from the compounded rubber during the vulcanization process and at the time of use under high temperature, and as a result of crosslinking, Shows the action.

First, the cross-linking causes a change in the volume and modulus of the adhesive layer before and after the cross-linking, and the greater the change, the lower the durability of the adhesive force. Since the cross-linking reaction particularly progresses at high temperatures, the adhesion deterioration at high temperatures becomes large.
Therefore, from this point, it is preferable that the butadiene component is small. Secondly, the cohesive failure resistance of the adhesive layer can be obtained by crosslinking the particles, and the interfacial bonding force can be obtained by crosslinking the particles and the polymer in the rubber between the adhesive layer and the rubber. Therefore, from this point, the butadiene component is necessary.

Therefore, the latex particles are constituted by a polymer having a different composition ratio in the same particle, which is obtained from a first monomer mixture having a low butadiene content and a second monomer mixture having a higher butadiene content. . That is, the particles obtained by polymerizing the second monomer mixture in the presence of the first polymer can sufficiently obtain the cohesive failure resistance of the adhesive layer and the interfacial bonding force between the adhesive layer and the rubber, and at the same time contain butadiene. Since the amount is small, the influence of the change in volume modulus is small, and the adhesive force, especially the durability can be improved.

When the second polymer is subsequently polymerized after the first polymer is polymerized, the first polymer having a low butadiene content is on the inner layer side of the particles. It is possible to reduce the influence on the second action.

From these points, the present inventor has made the latex particles, which used to have a substantially uniform structure, a heterogeneous structure having polymers having different monomer composition ratios in the same particle, and By increasing the weight ratio of the latex particles, the strength of the latex particles is improved, and at the same time, the curing of the adhesive layer following the latex vulcanization in the vulcanization process is prevented, and the heat resistance is greatly improved without impairing the adhesiveness. Made it possible to improve.

In order to make the copolymer particles have a structure composed of polymers having different composition ratios, the charging ratio of the monomers constituting the vinylpyridine-styrene-butadiene terpolymer latex is changed during the polymerization. Can be done by

Specifically, after an emulsifier such as potassium rosinate is dissolved in water, the first monomer mixture mainly on the inner layer side is added thereto. Further, an electrolyte such as sodium phosphate and peroxides are added as an initiator to carry out polymerization. Then, after reaching a predetermined conversion rate, the second monomer mixture mainly on the outer layer side is added to continue the polymerization. afterwards,
After reaching a predetermined conversion rate, a charge transfer agent is added to terminate the polymerization, and the remaining monomers are removed to obtain a rubber latex having a structure composed of polymers having different composition ratios.

The composition ratio of the monomers constituting the produced rubber latex is measured by the NMR (nuclear magnetic resonance) method and the weight composition ratio is obtained from the peak area of the chart, or the viscoelastic behavior of the polymer is determined. There is a method of measuring and determining the weight composition ratio from the loss.

When the content of vinylpyridine in the first monomer mixture of the vinylpyridine-styrene-butadiene terpolymer latex in the adhesive composition is less than 5% by weight, the adhesive strength of the entire adhesive composition is low. Is not preferable, and conversely, when it exceeds 15% by weight, the vulcanization reaction of the latex is promoted, which is not preferable. When the content of styrene is less than 40% by weight, the strength of the latex particles decreases, leading to a decrease in the strength of the adhesive layer and eventually the adhesive strength. On the other hand, when it exceeds 70% by weight, the latex particles become hard. If the product is used under high strain, the adhesive strength will be severely deteriorated. Regarding butadiene, if the content is less than 15% by weight, the amount of cross-linking is reduced and the adhesive strength is reduced, and if it exceeds 55% by weight, the latex vulcanization reaction proceeds rapidly, which is not preferable.

In the second monomer mixture, when the content of vinylpyridine is less than 5% by weight, the adhesive strength of the entire adhesive composition is reduced as described above, and when it exceeds 20% by weight, the adhesive composition is Becomes brittle, which is not preferable. When the content of styrene is less than 10% by weight, the strength of the latex particles and the adhesive layer is lowered, the adhesive strength is lowered, and conversely,
If it exceeds 40% by weight, the co-vulcanizability of the adhesive layer and the adhered rubber is lowered, and the adhesive strength is also lowered, which is not preferable. Regarding the content of butadiene, if the content is less than 45% by weight, the adhesive becomes too hard, and if it exceeds 75% by weight,
On the contrary, the adhesive becomes too soft, which is not preferable.

Further, regarding the ratio of the polymer obtained by the first monomer mixture to the polymer obtained by the second monomer mixture, when the amount of the former polymer was too small, the initial adhesiveness was good. However, the heat resistance decreases, and on the contrary,
If the amount becomes too large, the initial adhesive strength will decrease.

In the adhesive composition of the present invention, the solid content weight ratio of the mixture of the co-condensation resin, the terpolymer latex and the resorcin-formaldehyde precondensate has the following formula (A) / {(B ) + (C)} = 10/100 to 125 /
100 (C) / (B) = 2.5 / 100 to 25/100 (In the formula, A represents the solid content weight of the co-condensed resin, and B represents the solid content weight of the terpolymer latex. , C represents the solid content weight of the above-mentioned resorcinol-formaldehyde initial condensate.), But when the value of the former formula is less than 10/100, the strength of the adhesive layer is And the adhesive strength is lowered, which is not preferable. 1
When it exceeds 25/100, the adhesive layer becomes hard and brittle, the bonding force with the adherend rubber is lowered, the adhesive force is lowered, and the cord subjected to the adhesive treatment becomes hard, which is not preferable because it is difficult to handle. If the value of the latter formula is less than 2.5 / 100, the reinforcing effect on the latex is small and the strength of the adhesive layer becomes insufficient, resulting in a decrease in adhesive strength, which is not preferable. On the other hand, when it exceeds 25/100, the adhesive layer becomes hard and brittle, the bonding force with the adhered rubber decreases, the adhesive force decreases, and the adhesive-treated cord becomes hard, which makes the handling difficult, Not preferable.

The adhesive composition according to the present invention is adhered to a fiber material such as polyester fiber, subjected to an appropriate heat treatment to treat the adhesive composition, and embedded in unvulcanized rubber to be vulcanized. This makes it possible to firmly bond the fiber and the rubber.

The polyester fibers that can be used in the present invention are
A linear polymer having an ester bond in the main chain, and 25% or more of the bond modes in the main chain are preferably ester bond modes. Examples of glycols include ethylene glycol, propylene glycol, butylene glycol, methoxy polyethylene glycol, pentaerythritol and the like. On the other hand, the dicarboxylic acids are obtained by condensation of terephthalic acid, isophthalic acid and their dimethyl compounds by esterification reaction or transesterification reaction. The most typical fiber material is polyethylene terephthalate.

The adhesive composition of the present invention contains, in addition to the polyester fibers as described above, aliphatic polyamide fibers such as rayon, vinylon, 6-nylon, 6,6-nylon, and 4,6-nylon, and paraffin. It can be used for aromatic polyamide fibers typified by phenylene terephthalamide, and all fiber materials used for reinforcing rubber products such as inorganic fibers typified by carbon fibers and glass fibers.

Further, regarding those processed with an epoxy compound or an isocyanate compound during or after the polymerization / spinning process of the fiber, or the fiber material previously processed with an electron beam, microwave, corona discharge, plasma treatment or the like. Also, the adhesive composition of the present invention can be applied.

The polyester fiber material is a cord,
It may be in any form such as a cable, a filament, a filament chip, a cord fabric, and a canvas. Further, the adhesive composition of the present invention can be applied to all rubber products such as tires, conveyor belts, belts, hoses and air springs.

As a method for adhering the adhesive composition to the fiber material, a method of dipping the fiber material in an adhesive composition liquid, a method of applying the adhesive composition by brush, a method of spraying the adhesive composition, etc. However, an appropriate method can be selected as needed.

The heat treatment carried out subsequent to the drying is preferably carried out at a temperature not lower than the glass transition temperature of the polymer of the fiber material, preferably not lower than [melting temperature minus 70 ° C.] and lower than [melting temperature minus 20 ° C.]. preferable. The reason for this is that at a temperature below the glass transition temperature of the polymer, the molecular mobility of the polymer is poor, and the cocondensation resin and the polymer in the adhesive composition cannot perform sufficient interaction,
This is because the bonding force between the adhesive composition and the fiber material cannot be obtained. Further, since the fiber material and the rubber latex in the adhesive composition are deteriorated at a temperature of [melting temperature minus 20 ° C.] or higher of the polymer, and at a temperature of 250 ° C. or higher, decomposition of a part of the co-condensed resin starts. Not preferable.

The reason why this adhesive composition is particularly suitable for the adhesion between the polyester fiber material and the rubber is that the co-condensation resin obtained by co-condensing m-cresol and m-aminophenol with formaldehyde is used for polyester fibers. Since it has good solubility and diffusivity, it can diffuse and bind to an extremely large amount on the polyester surface.
All of the monomers constituting the co-condensation resin are highly functional to the resorcinol-formaldehyde initial condensate or the methylene donor because each of the monomers constituting the co-condensation resin is trifunctional with respect to the methylolation reaction and methylene bridge, and is efficiently resinified. This is because.

Further, since the latex having the above-mentioned non-uniform structure is used, the curing of the adhesive layer during the vulcanization process and the reduction of the strength of the adhesive layer at high temperature are suppressed, and as a result, the adhesive strength is maintained even at high temperature. Is high, and adhesion deterioration during continuous use under high temperature and high strain,
And the strength deterioration of the fiber material is extremely reduced. Furthermore,
The adhesive composition using this co-condensation resin has very little toxicity and is extremely useful from the viewpoint of environmental pollution.

[0053]

According to the present invention, since a latex having a non-uniform structure is used, the curing of the adhesive layer during the vulcanization process and the reduction of the strength of the adhesive layer at high temperature are suppressed. The adhesive strength is high even under the temperature, and the adhesive deterioration during continuous use under high temperature and high strain and the strength deterioration of the fiber material are extremely reduced. On the other hand, the adhesive composition using the co-condensation resin according to the present invention has extremely little toxicity and is extremely useful from the viewpoint of environmental pollution.

[0054]

EXAMPLES The present invention is described in Examples 1-28 and Comparative Examples 1-27.
It will be described in detail based on. For each example and comparative example,
The adhesive composition comprising the caustic soda aqueous solution of the co-condensation resin described in Table 1 and the RFL liquid described in Table 2 is used.
As the vinyl pyridine-styrene-butadiene copolymer latex therein, the latex having a uniform structure or a non-uniform structure shown in Tables 3 to 10 is used.

Examples 1 to 18 (1) Preparation of co-condensed resin (a) In a reactor equipped with a thermometer, a stirrer, a reflux condenser, and a dropping funnel, 200 parts by weight of m-cresol (1.
85 mol), 100 parts by weight of water, and 0.47 parts by weight of calcium hydroxide were charged, and the mixture was stirred at 60 ° C. with stirring at 0.
189 parts by weight of 37% formalin (2.32 over 5 hours)
(Mol) was added dropwise, and stirring was continued at the same temperature for 4.5 hours to carry out the resolization reaction. (B) Next, 213 parts of m-aminophenol (1.95)
(Mol) was charged, and stirring was continued at 100 ° C. for 4 hours to carry out a novolak reaction. (C) Thereafter, the temperature was raised to 160 ° C., and heat treatment was performed at 160 ° C. for 1.5 hours while purging with N ₂ gas to convert the unreacted monomer into a novolak. (D) Next, the temperature is raised to 200 ° C., the unreacted monomers are distilled off under reduced pressure of 5 torr for 0.5 hours, and the target novolac-type m-cresol / m-aminophenol / formaldehyde co-condensation is performed. A resin was obtained. (E) The composition of the obtained co-condensation resin is such that the monomers are 9%, 4
The content of nucleophiles and above was 65%, the co-condensation molar ratio of constituent monomers was m-cresol / m-aminophenol = 0.97, and the softening point was 121 ° C. (F) This co-condensed resin was made into a caustic soda aqueous solution according to Table 1.

(2) Preparation of RFL Solution Using the latexes listed in Tables 3 to 10, the latexes were blended according to Table 2 and aged at 25 ° C. for 24 hours to prepare an RFL solution.

(3) Preparation of Adhesive Composition An adhesive composition was prepared by mixing 73.1 parts by weight of the RFL solution with 23.1 parts by weight of an aqueous caustic soda solution of the co-condensed resin.

[0058]

[Table 1] Co-condensation resin 20.0 parts by weight Caustic soda 1.2 parts by weight Water 78.8 parts by weight

[0059]

[Table 2] Water 520.6 parts by weight Resorcin 14.5 parts by weight Formalin (37%) 18.5 parts by weight Caustic soda (10%) 10.5 parts by weight Vinylpyridine-styrene-435.9 parts by weight Butadiene copolymer latex

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

[Table 9]

[0067]

[Table 10]

(4) Treatment of cord adhesive composition As a polyester fiber material, a twist structure of 1500 d / 2,
A polyethylene terephthalate tire cord having an upper twist number of 40 turns / 10 cm and a lower twist number of 40 turns / 10 cm is used. The cord was dipped in the adhesive composition, dried at 150 ° C. for 1.5 minutes, and then heat-treated for 2 minutes in an atmosphere kept at 240 ° C.

(5) Measurement of initial adhesive strength The above-mentioned adhesive composition treatment cord was embedded in an unvulcanized rubber composition having the composition shown in Table 11, and 170 ° C. × 30 minutes, 20 kg /
Vulcanized under the condition of cm ² . The cord was dug up from the obtained vulcanized rubber, and the drag force at the time of peeling the cord from the vulcanized rubber was measured at a speed of 30 cm / min.
The results are shown in Tables 3-10.

(6) Measurement of heat-resistant adhesive strength The above adhesive composition treatment cord was embedded in an unvulcanized rubber composition having the composition shown in Table 11, and 190 ° C. × 30 minutes, 20 kg /
Vulcanized under the condition of cm ² . The resistance at the time of peeling was measured by the same method, and this was taken as the heat resistant adhesive strength. The results are shown in Tables 3-10.

[0071]

[Table 11] Natural rubber 80 parts by weight Styrene butadiene copolymer rubber 20 parts by weight Carbon black 40 parts by weight Stearic acid 2 parts by weight Petroleum softener 10 parts by weight Baintar 4 parts by weight Zinc white 5 parts by weight N-phenyl-B-naphthylamine 1.5 parts by weight 2-benzothiazyl disulfide 0.75 parts by weight Diphenylguanidine 0.75 parts by weight Sulfur 2.5 parts by weight

Example 19 (1) Preparation of co-condensation resin (a) and (b) were carried out in the same manner as in Examples 1 to 18 above. (C) After that, the temperature was raised to 160 ° C., and heat treatment was performed at 160 ° C. for 100 minutes while purging with N ₂ gas. (D) Next, the unreacted monomer was distilled off under reduced pressure of 1 Torr for 1.0 hour to obtain the target m-cresol / m-aminophenol / formaldehyde co-condensation resin. (E) The composition of the obtained co-condensation resin has a monomer content of 1.0%.
In the following, the content of tetranuclear or higher is 61%, the co-condensation molar ratio of constituent monomers is m-cresol / m-aminophenol = 0.
It was 99. (F) was performed in the same manner as in Examples 1 to 18 above. Also,
(2) Preparation of RFL liquid, (3) Preparation of adhesive composition,
The same applies to Examples 1 to 18 regarding (4) cord adhesive composition treatment, (5) initial adhesive strength measurement, and (6) heat resistant adhesive strength measurement.

Example 20 (1) Preparation of co-condensation resin (a) to (f) were carried out in the same manner as in Examples 1 to 18 above. (2) Preparation of RFL liquid The same procedure as in Example 2 was performed. (3) Preparation of Adhesive Composition An adhesive composition was prepared by mixing 90.9 parts by weight of the RFL solution with 9.1 parts by weight of an aqueous caustic soda solution of the co-condensed resin. In addition, (4) cord adhesive composition treatment,
(5) Measurement of initial adhesive strength and (6) Measurement of heat resistant adhesive strength are the same as in Examples 1-18.

Example 21 (1) Preparation of co-condensation resin (a) to (f) were carried out in the same manner as in Examples 1 to 18 above. (2) Preparation of RFL liquid The same procedure as in Example 2 was performed. (3) Preparation of Adhesive Composition An adhesive composition was prepared by mixing 67.5 parts by weight of the RFL solution with 37.5 parts by weight of an aqueous solution of the cocondensation resin in sodium hydroxide. In addition, (4) cord adhesive composition treatment,
(5) Measurement of initial adhesive strength and (6) Measurement of heat resistant adhesive strength are the same as in Examples 1-18.

Example 22 (1) Preparation of co-condensation resin (a) to (f) were carried out in the same manner as in Examples 1 to 18 above. (2) Preparation of RFL liquid The same procedure as in Example 2 was performed. (3) Preparation of Adhesive Composition An adhesive composition was prepared by mixing 45.5 parts by weight of the RFL solution with 55.5 parts by weight of a caustic soda aqueous solution of the co-condensation resin. In addition, (4) cord adhesive composition treatment,
(5) Measurement of initial adhesive strength and (6) Measurement of heat resistant adhesive strength are the same as in Examples 1-18.

Example 23 (1) Preparation of co-condensation resin (a) to (f) were carried out in the same manner as in Examples 1 to 18. (2) Preparation of RFL Solution Using the same latex as in Example 2, the compounds were blended according to Table 12, and aged at 25 ° C. for 24 hours to prepare an RFL solution.

[0077]

[Table 12] Water 511.3 parts by weight Resorcin 3.3 parts by weight Formalin (37%) 4.3 parts by weight Caustic soda (10%) 2.4 parts by weight Vinyl pyridine-styrene-478.7 parts by weight Butadiene copolymer latex

(3) Preparation of Adhesive Composition An adhesive composition was prepared by mixing 73.1 parts by weight of the RFL solution with 23.1 parts by weight of an aqueous caustic soda solution of the co-condensed resin. In addition, (4) cord adhesive composition treatment,
(5) Measurement of initial adhesive strength and (6) Measurement of heat resistant adhesive strength are the same as in Examples 1-18.

Example 24 (1) Preparation of co-condensation resin (a) to (f) were carried out in the same manner as in Examples 1 to 18. (2) Preparation of RFL liquid Using the same latex as in Example 2, the compounds were blended according to Table 13 and aged at 25 ° C. for 24 hours to prepare an RFL liquid.

[0080]

[Table 13] Water 513.7 parts by weight Resorcin 5.5 parts by weight Formalin (37%) 8.3 parts by weight Caustic soda (10%) 4.7 parts by weight Vinylpyridine-styrene-466.8 parts by weight Butadiene copolymer latex

(3) Preparation of adhesive composition An adhesive composition was prepared by mixing 73.1 parts by weight of the RFL solution with 23.1 parts by weight of an aqueous caustic soda solution of the co-condensed resin. In addition, (4) cord adhesive composition treatment,
(5) Measurement of initial adhesive strength and (6) Measurement of heat resistant adhesive strength are the same as in Examples 1-18.

Example 25 (1) Preparation of co-condensed resin (a) to (f) were carried out in the same manner as in Examples 1 to 18. (2) Preparation of RFL solution Using the same latex as in Example 2, blended according to Table 14 and aged at 25 ° C for 24 hours to prepare an RFL solution.

[0083]

[Table 14] Water 529.5 parts by weight Resorcin 27.1 parts by weight Formalin (37%) 34.8 parts by weight Caustic soda (10%) 19.6 parts by weight Vinylpyridine-styrene-389.2 parts by weight Butadiene copolymer latex

(3) Preparation of Adhesive Composition An adhesive composition was prepared by mixing 73.1 parts by weight of the RFL solution with 23.1 parts by weight of an aqueous caustic soda solution of the co-condensed resin. In addition, (4) cord adhesive composition treatment,
(5) Measurement of initial adhesive strength and (6) Measurement of heat resistant adhesive strength are the same as in Examples 1-18.

Example 26 (1) Preparation of co-condensation resin (a) The same procedure as in Examples 1 to 18 was carried out, except that 165 parts by weight of formalin was added dropwise. (B) The same procedure as in Examples 1 to 18 was repeated except that the amount of m-aminophenol charged was 283 parts by weight. (C) and (d) were performed in the same manner as in Examples 1-18. (E) The composition of the obtained co-condensation resin has a monomer content of 9.0.
%, Content of tetranuclear compounds of 35% or more, co-condensation molar ratio of constituent monomers m-cresol / m-aminophenol = 1.0
It was 0. (F) was performed in the same manner as in Examples 1 to 18 above. Further, (2) adjustment of RFL liquid, (3) adjustment of adhesive composition, (4) treatment of adhesive composition of cord, (5) measurement of initial adhesive strength, and (6) measurement of heat resistant adhesive strength, The same applies to the second embodiment.

Example 27 (1) Preparation of co-condensation resin (a) The same procedure as in Examples 1 to 18 was carried out except that 300 parts by weight of formalin was added dropwise. (B) The procedure of Examples 1 to 18 was repeated except that the amount of m-aminophenol charged was 506 parts by weight. (C) and (d) were performed in the same manner as in Examples 1-18. (E) The composition of the obtained co-condensation resin has a monomer of 8.0.
%, Tetranuclear or higher content 62%, co-condensation molar ratio of constituent monomers m-cresol / m-aminophenol = 0.5
It was 0. (F) was performed in the same manner as in Examples 1 to 18 above. Further, (2) adjustment of RFL liquid, (3) adjustment of adhesive composition, (4) treatment of adhesive composition of cord, (5) measurement of initial adhesive strength, and (6) measurement of heat resistant adhesive strength, The same applies to the second embodiment.

Example 28 (1) Preparation of co-condensed resin (a) The same procedure as in Examples 1 to 18 was carried out except that 148 parts by weight of formalin was added dropwise. (B) The same procedure as in Examples 1 to 18 was performed except that the amount of m-aminophenol charged was 181 parts by weight. (C) and (d) were performed in the same manner as in Examples 1-18. (E) The composition of the obtained co-condensation resin is monomer 10.0.
%, Tetranuclear or more content 64%, co-condensation molar ratio of constituent monomers m-cresol / m-aminophenol = 2.0
It was 0. (F) was performed in the same manner as in Examples 1 to 18 above. Further, (2) adjustment of RFL liquid, (3) adjustment of adhesive composition, (4) treatment of adhesive composition of cord, (5) measurement of initial adhesive strength, and (6) measurement of heat resistant adhesive strength, The same applies to the second embodiment.

Comparative Examples 1 to 17 The same as Examples 1 to 18 except that the particle structure of the latex differs according to Tables 3 to 10.

Comparative Example 18 (1) The heat treatment described in (c) and (d) of Examples 1 to 18 was not carried out during the preparation of the co-condensed resin, and a product corresponding to (e) was obtained. The composition of the co-condensed resin
The same as Examples 1 to 18 except that the monomer content was 15%, the content of tetranuclear compounds was 68%, and the co-condensation molar ratio of constituent monomers was m-cresol / m-aminophenol = 1.08.

Comparative Example 19 (1) When adjusting the co-condensed resin, the residual monomer was removed by two times of toluene extraction without performing the heat treatment described in (c) and (d) of Examples 1 to 18, m-Cresol / m-aminophenol / formaldehyde co-condensation resin was obtained, and the composition of the obtained co-condensation resin corresponding to (e) had a monomer content of 3.2% and a tetranuclear or higher content rate of 71.
%, Co-condensation molar ratio of constituent monomers m-cresol / m-
The same as Examples 1 to 18 except that aminophenol = 1.02.

Comparative Example 20 (1) Preparation of Co-condensed Resin (a) to (c) were carried out in the same manner as in Examples 1 to 18. (D) Residual monomers were removed by extracting twice with toluene to obtain m-cresol / m-aminophenol / formaldehyde co-condensation resin. (E) The composition of the obtained co-condensation resin is monomer 10.0.
%, The content of tetranuclear compounds was 71%, and the cocondensation ratio of constituent monomers was m-cresol / m-aminophenol = 1.02. Further, (2) adjustment of RFL liquid, (3) adjustment of adhesive composition, (4) treatment of adhesive composition of cord, (5) measurement of initial adhesive strength, and (6) measurement of heat resistant adhesive strength, The same applies to the second embodiment.

Comparative Example 21 (1) Preparation of Cocondensation Resin (a) to (f) were carried out in the same manner as in Examples 1 to 18. (2) Preparation of RFL liquid The same procedure as in Example 2 was performed. (3) Preparation of Adhesive Composition Example 1 except that 93.0 parts by weight of the RFL solution was mixed with 7.0 parts by weight of the caustic soda aqueous solution of the co-condensation resin.
An adhesive composition was prepared in the same manner as described above. Also,
Examples (1) to (4) cord adhesive composition treatment, (5) initial adhesive strength measurement, and (6) heat resistant adhesive strength measurement
Similar to 18.

Comparative Example 22 (1) Preparation of Cocondensation Resin (a) to (f) were carried out in the same manner as in Examples 1 to 18. (2) Preparation of RFL liquid The same procedure as in Example 2 was performed. (3) Preparation of Adhesive Composition An adhesive composition was prepared in the same manner as in Examples 1 to 18 except that 43.5 parts by weight of the RFL solution was mixed with 56.5 parts by weight of an aqueous caustic soda solution of the co-condensation resin. It was a thing. Also,
Examples (1) to (4) cord adhesive composition treatment, (5) initial adhesive strength measurement, and (6) heat resistant adhesive strength measurement
Similar to 18.

Comparative Example 23 (1) Preparation of Cocondensation Resin (a) to (f) were carried out in the same manner as in Examples 1 to 18. (2) Preparation of RFL solution Using the same latex as in Example 2, blended according to Table 15, and aged at 25 ° C for 24 hours to prepare an RFL solution.

[0095]

[Table 15] Water 509.6 parts by weight Resorcin 1.4 parts by weight Formalin (37%) 1.7 parts by weight Caustic soda (10%) 1.0 parts by weight Vinylpyridine-styrene-486.1 parts by weight Butadiene copolymer latex

(3) Preparation of Adhesive Composition An adhesive composition was prepared by mixing 73.1 parts by weight of the caustic soda aqueous solution of the co-condensation resin with 76.9 parts by weight of the RFL solution. In addition, (4) cord adhesive composition treatment,
(5) Measurement of initial adhesive strength and (6) Measurement of heat resistant adhesive strength are the same as in Examples 1-18.

Comparative Example 24 (1) Preparation of Cocondensation Resin (a) to (f) were carried out in the same manner as in Examples 1 to 18. (2) Preparation of RFL Solution Using the same latex as in Example 2, the compounds were blended according to Table 16 and aged at 25 ° C. for 24 hours to prepare an RFL solution.

[0098]

[Table 16] Water 591.2 parts by weight Resorcin 29.2 parts by weight Formalin (37%) 37.3 parts by weight Caustic soda (10%) 21.1 parts by weight Vinylpyridine-styrene-381.2 parts by weight Butadiene copolymer latex

(3) Preparation of Adhesive Composition An adhesive composition was prepared by mixing 73.1 parts by weight of the RFL solution with 23.1 parts by weight of an aqueous caustic soda solution of the co-condensed resin. In addition, (4) cord adhesive composition treatment,
(5) Measurement of initial adhesive strength and (6) Measurement of heat resistant adhesive strength are the same as in Examples 1-18.

Comparative Example 25 (1) Preparation of co-condensed resin (a) The same procedure as in Examples 1 to 18 was carried out except that 145 parts by weight of formalin was added dropwise. (B) The same procedure as in Examples 1 to 18 was repeated except that the amount of m-aminophenol charged was 283 parts by weight. (C) and (d) were performed in the same manner as in Examples 1-18. (E) The composition of the obtained co-condensation resin has a monomer content of 9.0.
%, Tetranuclear or more content 30%, co-condensation molar ratio of constituent monomers m-cresol / m-aminophenol = 0.9
It was 8. (F) was performed in the same manner as in Examples 1 to 18 above. Further, (2) adjustment of RFL liquid, (3) adjustment of adhesive composition, (4) treatment of adhesive composition of cord, (5) measurement of initial adhesive strength, and (6) measurement of heat resistant adhesive strength, The same applies to the second embodiment.

Comparative Example 26 (1) Preparation of Co-condensation Resin (a) The same procedure as in Examples 1 to 18 was carried out except that 300 parts by weight of formalin was added dropwise. (B) The same procedure as in Examples 1 to 18 was performed except that the amount of m-aminophenol charged was 606 parts by weight. (C) and (d) were performed in the same manner as in Examples 1-18. (E) The composition of the obtained co-condensation resin is monomer 10.0.
%, Tetranuclear or higher content 63%, co-condensation molar ratio of constituent monomers m-cresol / m-aminophenol = 0.3
It was 8. (F) was performed in the same manner as in Examples 1 to 18 above. Further, (2) adjustment of RFL liquid, (3) adjustment of adhesive composition, (4) treatment of adhesive composition of cord, (5) measurement of initial adhesive strength, and (6) measurement of heat resistant adhesive strength, The same applies to the second embodiment.

Comparative Example 27 (1) Preparation of Co-Condensed Resin (a) The same procedure as in Examples 1 to 18 was carried out except that 125 parts by weight of formalin was added dropwise. (B) The procedure of Examples 1 to 18 was repeated except that the amount of m-aminophenol charged was 148 parts by weight. (C) and (d) were performed in the same manner as in Examples 1-18. (E) The composition of the obtained co-condensation resin has a monomer of 11.0.
%, Tetranuclear or more content 60%, co-condensation molar ratio of constituent monomers m-cresol / m-aminophenol = 2.1
It was 2. (F) was performed in the same manner as in Examples 1 to 18 above. Further, (2) adjustment of RFL liquid, (3) adjustment of adhesive composition, (4) treatment of adhesive composition of cord, (5) measurement of initial adhesive strength, and (6) measurement of heat resistant adhesive strength, The same applies to the second embodiment.

The following can be seen from the results of the examples. (1) Examples 1 to 18 and Comparative Examples 1 to 17 under the same experimental conditions
Regarding is as follows. (A) In Comparative Example 3, Examples 1 to 4 and Comparative Example 9, the weight ratio of the first polymer to the second polymer was changed. This shows that even if the composition ratio of the polymers is the same, if the weight ratio is different, both the initial adhesive strength and the heat resistant adhesive strength are affected. (B) Comparative Examples 1, 2, 4 to 8 have different composition ratios in a uniform structure. From this, it can be seen that the adhesive force is affected by the composition ratio even with the same uniform structure.

(C) Comparative Examples 2 and 3 compare the uniform structure and the non-uniform structure. From this, it can be seen that the adhesive force is different due to the difference in structure even if the total composition ratio of the polymer is the same. The same applies to Comparative Example 4, Example 1; Comparative Example 5, Example 2; Comparative Example 6, Example 3; Comparative Example 7, Example 4; Comparative Example 8 and Comparative Example 9.
In Comparative Example 9, it is considered that the influence of the weight ratio of the polymer strongly appeared. (D) Comparative Example 10, Examples 5, 6, 2, 7 and Example 11
Increases the styrene content of the first polymer in this order,
The butadiene content is reduced. This shows that even if the weight ratio of the polymer and the composition ratio of the second polymer are the same, the adhesive force is affected by the change of the composition ratio of the first polymer.

(E) Comparative Example 12, Examples 8, 9, 10,
In Nos. 2 and 11, and Comparative Example 13, the vinylpyridine content of the first polymer was increased and the butadiene content was decreased in this order. The same applies to this. (F) Comparative Example 14, Examples 12, 2, 13, 14, 1
In Comparative Example 5 and Comparative Example 15, the styrene content of the second polymer was increased and the butadiene content was decreased in this order. From this, it can be seen that even if the weight ratio of the polymer and the composition ratio of the first polymer are the same, the adhesive force is affected by the change of the composition ratio of the second polymer.

(G) Comparative Example 16, Examples 16 and 17,
2, 18 and Comparative Example 17 are those in which the vinylpyridine content of the second polymer was increased and the butadiene content was decreased in this order. The same applies to this.

(2) Example 2, Comparative Example 18, Example 1
9 and Comparative Example 19 are comparisons when the preparation method of the cocondensation resin is different. (H) In comparison between Example 2 and Comparative Example 18, Comparative Example 1
No. 8 did not undergo the step of further polymerizing the unreacted monomer and the step of removing it, and therefore, the residual amount of the monomer is large in the adhesive composition, which is considered to affect the adhesive strength. (I) In comparison between Example 2 and Example 19, Example 1
In No. 9, it is considered that the step of further polymerizing the unreacted monomer was carried out for a longer time, and the step of further removing the unreacted monomer was carried out under reduced pressure for a longer time, so that the residual amount of the monomer was small and the adhesive strength was improved. To be

(J) In the comparison between Example 2 and Comparative Examples 19 and 20, Comparative Example 19 was extracted with toluene as a residual monomer, so that the proportion of tetranuclear bodies was large, and it is considered that the adhesive strength was poor. (3) Comparative Example 21, Examples 20, 2, 21, 22 and Comparative Example 22 are examples in which the values of the formula (A) / {(B) + (C)} are different, and these values are also in accordance with the present invention. It turns out that it needs to be kept within range. (4) Comparative Example 23, Examples 23, 24, 2, 25, and Comparative Example 24 are examples in which the values of the formula (C) / (B) are different, and these values also need to be kept within the range of the present invention. I know there is. (5) Example 26, Comparative Examples 25 and 26, Examples 27 and 2
8, Comparative Example 27 is an example in which the monomer component and the co-condensation molar ratio are changed to 4 or more nuclides. It can be seen that each affects the adhesive strength.

[Brief description of drawings]

FIG. 1 is a GPC chart of a cocondensate.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 61/10 C08L 61/12 LMY 61/12 LMY C09J 161/04 JES C09J 161/04 JES 161/12 161 / 12 D06M 15/693 D06M 15/693 7310-4F B29C 67/14 X

Claims (2)

[Claims] 1. A co-condensation molar ratio obtained from (a) 1 H-NMR proton intensity ratio is 1: 0.5 to 1: 2,
In the molecular weight distribution determined by gel permeation chromatography (GPC), the area ratio obtained by the component in which four or more benzene rings are connected is in the range of 35% to 65%, and obtained by the monomer component. The area ratio is 10% or less, and it is via formaldehyde, m
-A co-condensation resin of cresol and m-aminophenol,
(B) Vinyl pyridine content 5 to 15% by weight, styrene content 40 to 70% by weight, and butadiene content 15
After polymerizing a first monomer mixture composed of ~ 55 wt%, vinylpyridine content 5-20 wt%, styrene content 10-40 wt%, and butadiene content 45-75 wt%. % Of the first polymer obtained by the first monomer mixture and the second polymer obtained by the second monomer mixture are polymerized from 50/50 to 80/20, vinylpyridine-styrene-butadiene terpolymer latex having polymers having different composition ratios in the same particle, and (c)
It contains a resorcin-formaldehyde initial condensate and has the following two formulas (A) / {(B) + (C)} = 10/100 to 125 /
100 (C) / (B) = 2.5 / 100 to 25/100 (In the formula, A represents the solid content weight of the co-condensed resin, and B represents the solid content weight of the terpolymer latex. , C represents the solid content weight of the resorcinol-formaldehyde initial condensate.), The adhesive composition. 2. (a) 0.5-2 mol of formaldehyde is added to 1 mol of m-cresol to resolate m-cresol at 20-100 ° C. in the presence of an alkali catalyst; (b) After adding 0.5 to 3 mol of m-aminophenol to the reaction mixture and novolacing at 70 to 130 ° C; (c) Furthermore, a constant temperature within a temperature range of 135 to 185 ° C under an inert gas atmosphere. And (d) heat treatment at a temperature of 130 to 220 ° C. under reduced pressure of 5 torr or less; and a co-condensation resin obtained by the heat treatment. The adhesive composition according to claim 1.