JPH08104780A - Latex composition for rock fiber aggregate, adhesive composition for rock fiber aggregate, and rock fiber aggregate - Google Patents

Abstract

PURPOSE: To obtain an adhesive composition which can impart sufficient strength and low residual compression strain to a rock fiber aggregate and is excellent in the operating characteristics in the production steps by mixing two copolymer latices each having a specified glass transition temperature. CONSTITUTION: This latex composition contains a copolymer latex (A) obtained by copolymerizing a mixture of 25-90wt.% conjugated diene monomer, 0.5-10wt.% ethylenically unsaturated carboxylic acid monomer and 0-74.5wt.% other copolymerizable monomer and having a glass transition temperature of -70 deg.C to below 30 deg.C, and a copolymer latex (B) obtained by copolymerizing a mixture of 60-99.5wt.% aromatic vinyl monomer, 0.5-10wt.% ethylenically unsaturated carboxylic acid monomer and 0-39.5wt.% copolymerizable other monomer and having a glass transition temperature of 30 deg.C to below 120 deg.C. The difference in glass transition temperature between the component A and the component B needs to be at least 40 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a latex composition for a rock fiber assembly, an adhesive composition for a rock fiber assembly, and a rock fiber assembly.

[0002]

2. Description of the Related Art Lock products are used for vehicle seats, chairs, sofas, beds, and water-permeable materials for civil engineering. Such a lock product is composed of a lock fiber aggregate in which various lock fibers such as palm, cotton, jute, polyester, nylon, polypropylene, aromatic polyamide, acrylic fiber or glass fiber are bulky bonded.
When bonding the lock fibers, an adhesive composition containing a copolymer latex is usually used. The copolymer latex used for the adhesive is required to have sufficient strength for the lock fiber aggregate and to have a property of reducing the compression residual strain of the lock fiber polymer. To meet such demands, an adhesive composition containing a copolymer latex obtained by using a specific oligomer as a polymerization emulsifier has been provided (Japanese Patent Publication No. 6-51869). The improvement of sex is insufficient and further improvement is required.

Further, the lock fiber aggregate is applied by spraying an adhesive composition containing a copolymer latex onto the lock fiber or by squeezing it with a roll after immersion, and then drying the lock fiber. Are joined and manufactured. Therefore, it is required that the adhesive containing the copolymer latex does not cause clogging of the spray nozzle and does not cause gum-up trouble on various rolls, that is, it has excellent operability. No one has been proposed that can satisfy even such demands.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventor in view of such circumstances, a latex containing a copolymer latex (A) and a copolymer latex (B) having a specific glass transition temperature is obtained. An adhesive composition containing a copolymer latex composition, wherein the copolymer latex composition has two different glass transition temperatures with a difference of 40 ° C. or more, It has been found that the aggregate has sufficient strength, the compressive residual strain is reduced, and the operability is excellent in the manufacturing process, and the present invention has been completed based on such findings.

[0005]

According to the present invention, therefore, 25 to 90% by weight of a conjugated diene monomer, 0.5 to 10% by weight of an ethylenically unsaturated carboxylic acid monomer, and copolymerizable therewith A copolymer latex obtained by copolymerizing a monomer mixture consisting of 0 to 74.5% by weight of another monomer, and having a glass transition temperature of -70 ° C or higher, 30
Acrylic vinyl monomer 60 to 99.5% by weight, ethylenically unsaturated carboxylic acid monomer 0.5 to 10% by weight, and copolymerizable with the copolymer latex (A) having a temperature of less than 0 ° C. Copolymer latex obtained by copolymerizing a monomer mixture consisting of 0 to 39.5% by weight of another monomer, and having a glass transition temperature of + 30 ° C or higher and lower than 120 ° C. A rock fiber aggregate comprising a combined latex (B), the copolymer latex composition having two different glass transition temperatures with a difference of 40 ° C. or more. A latex composition for use is provided.

The latex of the present invention contains a copolymer latex (A) and a copolymer latex (B). The copolymer latex (A) is a conjugated diene monomer 25.
To 90 wt%, preferably 30 to 75 wt%, ethylenically unsaturated carboxylic acid monomer 0.5 to 10 wt%, preferably 0.7 to 5 wt%, and other monomers copolymerizable therewith. It is a copolymer latex obtained by copolymerizing a monomer mixture of 0 to 74.5% by weight, preferably 0 to 69.3% by weight. When the amount of the ethylenically unsaturated carboxylic acid monomer is less than 0.5% by weight, the mechanical stability is poor, clogging of the spray or roll gum up occurs, and the adhesive strength decreases. On the contrary, if it exceeds 10% by weight, the viscosity becomes too high to be practical.

The conjugated diene monomer is 1,3-butadiene,
Isoprene, 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene and the like.

Examples of the ethylenically unsaturated carboxylic acid monomer include monocarboxylic acids such as acrylic acid and methacrylic acid; polycarboxylic acids such as maleic acid and fumaric acid;
Examples include polycarboxylic acid monoesters such as monobutyl fumarate, monobutyl maleate, and mono-2-hydroxypropyl maleate. These ethylenically unsaturated carboxylic acid monomers can also be used as alkali metal salts or ammonium salts. These ethylenically unsaturated carboxylic acid monomers may be used in combination of two or more kinds.

Other monomers copolymerizable with these are, for example, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 (Meth) acrylic acid ester monomers such as ethylhexyl (meth) acrylate, ethylenically unsaturated carboxylic acid amides such as (meth) acrylamide, N-methylol (meth) acrylamide, aromatics such as styrene and α-methylstyrene Examples thereof include vinyl monomers.

The glass transition temperature of the copolymer latex (A) is -70 ° C or higher and lower than 30 ° C, preferably -50 ° C or higher.
It is + 20 ° C. The glass transition temperature in the present invention means that measured by a differential calorimeter.

The copolymer latex (B) contains 60 to 99.5% by weight of an aromatic vinyl monomer, preferably 65 to 99.%.
3% by weight, ethylenically unsaturated carboxylic acid monomer 0.5 to
Monomer mixture consisting of 10% by weight, preferably 0.7 to 5% by weight, and 0 to 39.5% by weight, preferably 0 to 34.3% by weight of another monomer copolymerizable therewith. It is a copolymer latex obtained by copolymerizing When the amount of the ethylenically unsaturated carboxylic acid monomer is less than 0.5% by weight, the mechanical stability is poor, clogging of the spray or roll gum up occurs, and the adhesive strength decreases. On the contrary, if it exceeds 10% by weight, the viscosity becomes too high to be practical.

The aromatic vinyl monomer is an aromatic vinyl monomer such as styrene, α-methylstyrene, vinyltoluene, divinylbenzene and chlorostyrene.

Examples of the ethylenically unsaturated carboxylic acid monomer are the same as those mentioned above. Other monomers copolymerizable with these include (meth) acryl such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 ethylhexyl (meth) acrylate, and glycidyl (meth) acrylate. Examples thereof include acid ester monomers; conjugated diene monomers such as 1,3-butadiene and isoprene; and ethylenically unsaturated carboxylic acid amides such as (meth) acrylamide and N-methylol (meth) acrylamide. Among these, preferred are (meth) acrylic acid ester monomers and conjugated diene monomers. Further, these monomers may be used in combination of two or more kinds.

The glass transition temperature of the copolymer latex (B) is not less than + 30 ° C. and less than 120 ° C., preferably + 40 ° C.
~ + 115 ° C.

The copolymer latex composition of the present invention comprises a copolymer latex (A) and a copolymer latex (B), which have two different glass transition temperatures, and the two glass transition temperatures. Difference is 40 ° C. or more, preferably 50 to 150 ° C. When the difference between the two glass transition temperatures is less than 40 ° C., it is impossible to impart excellent strength to the resulting rock fiber aggregate and impart a small compressive residual strain.

The composition ratio of the copolymer latex (A) and the copolymer latex (B) is not unequivocally limited depending on the type of the copolymer latex, and the copolymer latex composition has two different glasses. The composition ratio is appropriately selected in such a range that it has a transition temperature and the difference between the two glass transition temperatures is 40 ° C. or higher. The composition of the copolymer latex composition is usually 20 to 80% by weight, preferably 30 to 70% by weight, and 80 to 20% by weight of the copolymer latex (B) in terms of solid content. %, Preferably 70 to 30% by weight.

The copolymer latex composition of the present invention may contain, in addition to the copolymer latexes (A) and (B), other polymers as long as the effects of the present invention are not impaired.
The amount of the other copolymer is usually 0 to 30% by weight based on the solid content in the copolymer latex composition.

The method for producing the copolymer latex used in the present invention is not particularly limited, and known emulsion polymerization can be used. For example, batch emulsion polymerization, semi-continuous emulsion polymerization, or continuous emulsion polymerization may be used. Alternatively, seed polymerization using a seed latex, multi-stage polymerization, or power feed polymerization in which the composition ratio of added monomer components or the like is changed continuously or intermittently can be used.

In these emulsion polymerizations, various known emulsifiers, polymerization initiators, chelating agents, electrolytes, dispersants, pH
A regulator or the like can be used. The polymerization temperature may be either high or low. Further, a known pH adjuster, dispersant, emulsifier, antiseptic, antifungal agent, antifoaming agent and the like can be added to the latex after the polymerization. It may also include a step of removing residual monomer from the polymerized latex or concentrating it.

The copolymer latex composition of the present invention can be used as it is or diluted with water as a lock fiber aggregate adhesive, but it is an adhesive composition blended with other additives. You can also As additives, known emulsifiers, dispersants, defoamers, antioxidants, ultraviolet absorbers, fillers, colorants, vulcanizing agents, vulcanization accelerators, crosslinking agents, auxiliary agents for crosslinking agents, preservatives, Thickeners, penetrants, flame retardants and the like are used. As a method for preparing the adhesive composition, a known method can be applied, and a method in which a latex, an additive and, if necessary, water are added to a tank and mixed with a stirrer is common. As a method for applying the obtained lock fiber aggregate adhesive to the lock fibers, known methods such as a dipping impregnation method, a spray method and a foaming method can be used.

The lock fiber assembly adhesive composition of the present invention can be applied to various lock fibers, for example, palm, cotton, jute, polyester, nylon, polypropylene, aromatic polyamide, acrylic fiber or glass fiber. Is mentioned. These lock fibers may be used alone or in combination of plural kinds of fibers. The fiber may be a new fiber produced from a fiber raw material, or may already be cut or woven for recycling use such as a rock fiber aggregate, a non-woven fabric or a woven fabric. Further, it is also possible to treat these rock fibers with the above-mentioned additive chemical liquid before applying the lock fiber aggregate adhesive composition, or after applying the adhesive agent, further treat with the above-mentioned additive chemical liquid. Generally, a lock fiber aggregate is obtained by applying a lock fiber aggregate adhesive composition to lock fibers and then drying with a hot air or the like. The drying method is not particularly limited, and a known method can be used.

The thus-obtained rock fiber aggregate is used as a material for rock products such as vehicle seats, chairs, sofas, beds, and water-permeable materials for civil engineering, and has excellent tensile strength, compressive strength and residual compression set. It is possible to provide rock products with excellent quality.

Various kinds of fibers such as palm, cotton, jute, polyester, nylon, polypropylene, aromatic polyamide, acrylic fiber or glass fiber are used as the type of lock fiber to which the adhesive for lock fiber assembly of the present invention can be applied. The fibers may be used alone or in combination of plural kinds of fibers. The fiber may be a new fiber produced from a fiber raw material, or may already be cut or woven for recycling use such as a rock fiber aggregate, a non-woven fabric or a woven fabric. Further, it is also possible to treat these lock fibers with the above-mentioned additive chemical liquid before applying the lock fiber aggregate adhesive agent, or to further treat with the above-mentioned additive chemical liquid after applying the adhesive agent. Generally, the lock fiber aggregate to which the lock fiber aggregate adhesive is applied is dried by hot air or the like. A known drying method can be used.

The thus-obtained rock fiber aggregate product is used for vehicle seats, chairs, sofas, beds, water-permeable materials for civil engineering, etc., and has excellent tensile strength and compressive strength, and further produces a small compressive residual strain. Therefore, it is possible to provide a lock product with excellent quality.

The preferred embodiments of the present invention will be described below. (1) The copolymer latex (A) is a conjugated diene monomer 3
0 to 75% by weight, 0.7 to 5% by weight of the ethylenically unsaturated carboxylic acid monomer, and 0 to 69.3% by weight of another monomer copolymerizable therewith. The latex composition for a lock fiber assembly of the present invention, which is a copolymer latex obtained by polymerization. (2) The glass transition temperature of the copolymer latex (A) is −
The latex composition for a lock fiber assembly according to the present invention, which has a temperature of 50 ° C to + 20 ° C. (3) Copolymer latex (B) is aromatic vinyl monomer 65 to 99.3 wt%, ethylenically unsaturated carboxylic acid monomer 0.7 to 5 wt%, and other copolymerizable with these The latex composition for a rock fiber assembly of the present invention, which is a copolymer latex obtained by copolymerizing a monomer mixture consisting of 0 to 34.3% by weight of the monomer. (4) The glass transition temperature of the copolymer latex (B) is +
The latex composition for a rock fiber assembly according to the present invention having a temperature of 40 ° C to + 115 ° C. (5) The latex composition for rock fiber aggregates of the present invention, wherein the difference between the two glass transition temperatures of the copolymer latex composition is 50 to 150 ° C. (6) The composition of the copolymer latex composition is 20 to 80% by weight of the copolymer latex (A) and 80 to 20% by weight of the copolymer latex (B) in terms of solid content. Latex composition for aggregates. (7) The composition of the copolymer latex composition is 30 to 70% by weight of the copolymer latex (A) and 70 to 30% by weight of the copolymer latex (B) in terms of solid content, and the lock fiber of the present invention. Latex composition for aggregates.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Parts and% in the examples and comparative examples are based on weight unless otherwise specified.

The glass transition temperature of the copolymer latex and the copolymer latex composition were measured, and the amount of agglomerates generated by a Marlon mechanical stability tester was measured by the following methods. (Measurement of glass transition temperature) The copolymer latex or the copolymer latex composition was placed in an aluminum dish and dried at room temperature, and then the water was sufficiently removed in a vacuum dryer to obtain a dried latex product. Seiko Instruments Inc. Thermal Analysis System SSC5200H Disk Statio
n, the glass transition temperature of 5 mg of the dried product of latex was measured using a differential thermogravimetric simultaneous measurement apparatus TG / DTA220 (measurement conditions: starting temperature −150 ° C., temperature rising rate 20 ° C.
/ Min).

(Measurement of Amount of Aggregate Generation) The copolymer latex and the copolymer latex composition were diluted with water to a solid content of 10% and filtered through a 100 mesh wire mesh. 100 g of the filtered latex was loaded with a Marlon mechanical stability tester (manufactured by Kumagai Riki) under a load of 15 kg and a rotational speed of 1000.
r. p. The test was conducted for 10 minutes. The diluted latex tested was filtered through a 100-mesh wire net, and the agglomerates collected on the 100-mesh wire net were dried in a hot air dryer at 110 ° C. for 3 hours, and the amount of dried agglomerates was measured.

Reference Example 1 Copolymer latex A1 to A3,
Production of B-1 to 2 and C-1 A polymerization vessel previously purged with nitrogen was charged with ion-exchanged water, an emulsifier, an inorganic salt, a chelating agent and a molecular weight modifier, and then the monomers shown in Table 1 were charged. Stirring was started, the contents were mixed, and the temperature was raised to 70 ° C. When the temperature in the polymerization vessel reached 70 ° C., a polymerization initiator dissolved in ion-exchanged water was separately injected into the polymerization vessel to start the polymerization reaction. The reaction was carried out for 15 hours while maintaining the temperature at 70 ° C., and water cooling was performed. The polymerization conversion rates were all over 98%. After removing the unreacted monomer of the obtained copolymer latex, the pH of the copolymer latex was adjusted to 7.0 with NaOH.

[0030]

[Table 1]

Example 1 The copolymer latex of Reference Example 1 was mixed to obtain each copolymer latex composition shown in Table 3. Table 2 shows the glass transition temperature of the copolymer latex composition and the amount of aggregates generated by a Marlon mechanical stability tester. An adhesive was prepared by diluting the copolymer latex composition with water to a solid content concentration of 10%. (Adhesion of lock fiber aggregate) Length 100 mm, width 100 m
m, thickness 30 mm, and weight 5 g of palm fiber aggregate, the above adhesive was spray-applied with 2 g of solid content from the front and back, and dried in a hot air dryer at 120 ° C. for 10 minutes to perform a palm lock test. Got a piece. Tensile strength and compressive residual strain were measured using these test pieces. The results are shown in Table 2.

Comparative Example 1 The copolymer latex of Reference Example 1 was mixed to obtain each copolymer latex composition shown in Table 2. Table 2 shows the glass transition temperature of each copolymer latex composition and the amount of aggregates produced by a Marlon mechanical stability tester. Each copolymer latex composition was diluted with water to a solid content concentration of 10% to prepare an adhesive, and test pieces were prepared in the same manner as above, and tensile strength and compression residual strain were measured. The results are shown in Table 2.

[0033]

[Table 2]

From Table 2, it can be seen that the adhesive composition containing the copolymer latex composition of the present invention can impart sufficient strength and low compressive residual strain to the rock fiber aggregate. From Table 2, it can be seen that when the difference in glass transition temperature of the copolymer latex composition is less than 40 ° C., the strength of the rock fiber aggregate becomes low and the compression residual strain becomes large (Experiment No. 2). −
7). It can be seen that when the copolymer latex composition has one glass transition temperature, the compressive residual strain becomes large (Experiment Nos. 2-8 and 2-9). It can be seen that when a monomer mixture containing no ethylenically unsaturated carboxylic acid monomer is used, mechanical stability becomes poor (Experiment No. 2-8, 2-9).

[0035]

As described above, by using the adhesive composition containing the latex of the present invention, it is possible to impart sufficient strength and a small compressive residual strain to the rock fiber aggregate, and the rock fiber aggregate. It is possible to bring excellent operability in the manufacturing process.

Claims (3)

[Claims] 1. A conjugated diene monomer of 25 to 90% by weight, an ethylenically unsaturated carboxylic acid monomer of 0.5 to 10% by weight, and other monomers copolymerizable with these 0 to 74.5% by weight. %
Is a copolymer latex obtained by copolymerizing a monomer mixture consisting of and having a glass transition temperature of -70 ° C.
As described above, a copolymer latex (A) having a temperature of less than 30 ° C.,
From 60 to 99.5% by weight of an aromatic vinyl monomer, 0.5 to 10% by weight of an ethylenically unsaturated carboxylic acid monomer, and 0 to 39.5% by weight of another monomer copolymerizable therewith. Is a copolymer latex obtained by copolymerizing the following monomer mixture, and has a glass transition temperature of + 30 ° C. or higher, 1
A latex composition comprising a copolymer latex (B) having a temperature of less than 20 ° C., wherein the copolymer latex composition has two different glass transition temperatures, the difference of which is 40 ° C. or more. A characteristic latex composition for rock fiber aggregates. 2. An adhesive composition for a lock fiber assembly, which comprises the latex composition for a lock fiber assembly according to claim 1. 3. A lock fiber assembly obtained by bonding with the adhesive composition for a lock fiber assembly according to claim 2.