JP2002212532A - Adhesive for adhesive interlining - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive excellent in adhesive force to various base fabrics and scarcely causing lowering of adhesive strength, particularly in clean ing with warm water and dry cleaning and an adhesive used as an underlayer water-based paste of double dot type adhesive interlining. SOLUTION: This adhesive for adhesive interlining is characterized by being water dispersion of a polyester resin composition having a polar group in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive for an adhesive interlining, which is excellent in adhesive strength to various base fabrics, and in particular, has a small decrease in adhesive strength during hot water cleaning and dry cleaning, especially a double dot type adhesive interlining. The present invention relates to an adhesive used as a lower aqueous paste.

[0002]

2. Description of the Related Art Conventionally, various interlinings have been used in clothes in order to reinforce the weakness of the fabric by utilizing the characteristics of the fabric. One of these interlinings is an adhesive interlining in which an adhesive is adhered to one surface of a fiber sheet. Traditionally,
In many cases, single-dot type adhesives for hot-melt adhesives bonded to fiber sheets were used for interlining, but in recent years, double-dot type adhesives, in which an aqueous paste is applied first and then the hot-melt adhesive is fixed, are the mainstream. It has become. The reason why the double dot type became mainstream is that the adhesive strength is higher than single dot, and the hot melt adhesive melted at the time of bonding with the surface cloth passes through the interlining and is used for ironing irons and hot press irons. The object is to reduce the phenomenon of adhesion (strike back).

As a resin for a double dot type lower layer aqueous paste, urethane type, acrylic type, polyethylene type, polyester type and the like have been proposed. Urethane-based adhesives have high adhesive strength and a small decrease in strength after dry cleaning, but a large decrease in strength after hot water cleaning.
In addition, weather resistance is poor and yellowing occurs with time.

Acrylics are inexpensive and have high adhesive strength,
There are problems such as seepage of the surfactant. Polyethylenes have limited combinations of hot melt adhesives and generally have low strength. As for the polyester type, what is obtained by dispersing crushed particles of polyester using a surfactant or the like has been studied. Polyester resins generally have high adhesive strength and high strength after cleaning with hot water, but the reduction in strength after dry cleaning is extremely large as compared with other resin systems, and there are few examples of actual use. However, with the trend in the cleaning industry from dry cleaning to hot water cleaning, expectations for polyester-based paste are increasing.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide:
An object of the present invention is to provide an adhesive for an adhesive interlining having excellent adhesive strength to various base fabrics and having a small decrease in adhesive strength during hot water cleaning and dry cleaning. In particular, an object of the present invention is to provide an adhesive used as a lower aqueous paste of a double dot type adhesive interlining.

[0006]

That is, the present invention relates to an adhesive for an adhesive interlining, which is an aqueous dispersion of a polyester resin composition having a polar group in a molecule.

[0007] The adhesive for the adhesive interlining is (1)
It is preferable to satisfy the requirement of (5). (1) The polar group of the polyester resin and the concentration thereof are (A) and / or (B) below. (A) 50 to 500 equivalents / 10 ⁶ g of sulfonic acid salt group (B) 200 equivalents / 10 ⁶ g or more of carboxyl group (2) Polycarboxylic acid component of polyester resin is converted from aromatic dicarboxylic acid 40 to 100 mol% Become. (3) The glass transition temperature of the polyester resin is 20 ° C. or higher. (4) The number average molecular weight of the polyester resin is 7000 or more. (5) The particle size of the aqueous dispersion particles is 1 μm or less.

The reason for having a polar group in the molecule is to suppress the decrease in strength after dry cleaning by introducing an appropriate hydrophilic component, and to form a fine particle by providing a self-emulsifying ability to form fine particles. This is for facilitating the penetration of the resin component into the resin and increasing the adhesive strength. That is, the polyester swells or dissolves in the dry cleaning liquid, so that the strength after dry cleaning is reduced. However, by giving appropriate hydrophilicity, swelling due to the dry cleaning liquid can be suppressed. Therefore, a decrease in strength after dry cleaning can be suppressed. Various surfactants can be used as a dispersion aid for obtaining an aqueous dispersion. However, precipitation on the surface occurs over time, which causes a decrease in adhesive strength. In order to obtain sufficient adhesive strength, 10
wt% or less, preferably 5 wt% or less, more preferably 2 wt% or less, still more preferably 1 wt% or less, particularly preferably 0.5 wt% or less, and most preferably 0.3 wt% or less.
% Should be used.

In order to introduce a polar group, a method of copolymerizing a component having a polar group with a dicarboxylic acid component or a glycol component in a polyester, a method of introducing a hydrophilic component such as an acrylic component by grafting, and the like are effective. is there.

Preferred examples of the polar group include an anionic polar group such as a sulfonate group, a sulfate group, a phosphate group and a carboxylate group, and a cationic polar group such as an ammonium base. The counter ion of the anionic group is preferably an alkali metal ion or an ammonium ion, and the counter ion of the cationic polar group is preferably a halogen ion or the like. Of these, sulfonic acid groups and carboxylic acid groups are particularly preferred.

The content of the polar group is preferably 20 equivalent / 10/10 in the case of a sulfonate group, a sulfate group, and a phosphate group.
⁶ g or more, more preferably 50 equivalents / 10 ⁶ g
Above, particularly preferably 70 equivalents / 10 ⁶ g or more, preferably 500 equivalents / 10 ⁶ g or less, more preferably 400 equivalents / 10 ⁶ g or less, particularly preferably 350 equivalents / 106 g or less.
Equivalent weight / 10 ⁶ g or less. In the case of a carboxylate group or an ammonium base, the amount is preferably 200 equivalents / 10 ⁶ g or more, more preferably 300 equivalents / 10 ⁶ g or more, particularly preferably 400 equivalents / 10 ⁶ g or less.
Is preferably from eq / 10 ⁶ g, more preferably 100
0 equivalent / 10 ⁶ g or less, particularly preferably 800 equivalent / 1
0 is ⁶ g or less.

When the content of the polar group is less than the above lower limit, it may be difficult to obtain a stable aqueous dispersion, or the effect of suppressing swelling in the dry cleaning liquid may be reduced. When the ratio is equal to or more than the above upper limit, the hydrophilicity is strong, and the strength decrease after cleaning with hot water may be large.

Further, the polycarboxylic acid component of the polyester resin used in the present invention is preferably composed of 40 to 100 mol% of an aromatic dicarboxylic acid. More preferably 60 to 100 mol%, further preferably 80 to 1
00 mol%. By using the aromatic dicarboxylic acid in such a range, swelling or dissolution of the resin due to the dry cleaning liquid can be suppressed, and a decrease in strength after dry cleaning can be prevented.

The polyester resin used in the present invention preferably has a glass transition temperature of 20 ° C. or higher. By setting the glass transition temperature to 20 ° C. or higher, a decrease in strength after cleaning with hot water can be prevented. Since the water dispersion of the present invention has good penetration into the base cloth, it has sufficient strength even at a glass transition temperature lower than the temperature used for cleaning with hot water, but hot water at a high temperature of 80 to 90 ° C. The glass transition temperature required to maintain the strength after cleaning is 20 ° C. or higher, preferably 40 ° C. or higher, more preferably 50 ° C. or higher.

The polyester resin used in the present invention preferably has a number average molecular weight of 7000 or more. By setting the number average molecular weight to 7000 or more, sufficient adhesiveness can be obtained. By keeping the molecular weight high, cohesive failure due to a decrease in cohesive strength of the adhesive can be prevented. The number average molecular weight is preferably 10,000 or more, more preferably 13,000 or more, and still more preferably 150 or more.
00 or more. The upper limit is not specified, but 20
0000 or less.

The polyester resin used in the present invention may be modified with urethane, epoxy or the like. In addition, melamine type, benzoguanamine type, isocyanate type, oxazoline type, epoxy type,
By using various hardening agents such as phenols, the strength of the resin can be further increased.

The particle size of the aqueous dispersion particles of the polyester resin used in the present invention is preferably 1 μm or less. This is because by making the particle size 1 μm or less, it is easy to permeate into the base fabric, and the strength is reduced after warm water cleaning and after dry cleaning.
The particle size is preferably 500 nm or less, more preferably 30 nm or less.
0 nm or less, more preferably 150 nm or less.

As the polyester used as the adhesive of the present invention, various raw materials can be used within the above range. As the dicarboxylic acid at that time, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 4,4′-diphenyldicarboxylic acid, 2,2′-diphenyldicarboxylic acid, ,
Aromatic dibasic acids such as 4'-diphenyl ether dicarboxylic acid, adipic acid, azelaic acid, sebacic acid, 1,4
-Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid, fumaric acid, maleic acid, itaconic acid and the like can be used. As the polyvalent carboxylic acid component, trimellitic anhydride, pyromellitic anhydride and the like can be used.

As the glycol component, ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-
Butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol,
Dipropylene glycol, 2,2,4-trimethyl-
1,3-pentanediol, cyclohexane dimethanol, tricyclodecane dimethanol, neopentyl glycol hydroxypivalate, bisphenol A ethylene oxide adduct and propylene oxide adduct, hydrogenated bisphenol A ethylene oxide adduct and propylene oxide Additives, 1,9
-Nonanediol, 2-methyloctanediol, 1,
10-dodecanediol, 2-butyl-2-ethyl-
Diols such as 1,3-propanediol and tricyclodecane dimethanol, and polyhydric alcohols such as trimethylolpropane can be used.

When a sulfonate group is introduced into a molecule, for example, 5-Na sulfoisophthalic acid, 5-ammonium sulfoisophthalic acid, 4-Na sulfoisophthalic acid, 4-methylammonium sulfoisophthalic acid,
Na sulfoterephthalic acid, 5-K sulfoisophthalic acid,
Alkali metal sulfonate or amine sulfonate compounds such as 4-K sulfoisophthalic acid, 2-K sulfoterephthalic acid, and Na sulfosuccinic acid, Na sulfonate
Salt-containing bisphenol A-alkylene oxide adducts, sulfonic acid K base-containing hydroquinone alkylene oxide adducts, and the like can be used.

When a carboxylate group is introduced into the molecule, for example, a compound such as trimellitic anhydride, trimellitic acid, pyromellitic anhydride, pyromellitic acid, trimesic acid, cyclobutanetetracarboxylic acid, dimethylolpropionic acid or the like is used. A method of neutralizing an unreacted carboxyl group with an amino compound, ammonia, an alkali metal or the like is used.

In order to introduce the acrylic component by grafting, a method of reacting a vinyl monomer having hydrophilicity with a radical initiator in a solution of a polyester composed of the above monomers is employed. Particularly, in this case, if a dicarboxylic acid of the polyester containing an unsaturated bond such as dimer acid, fumaric acid, maleic acid or itaconic acid is used, the grafting efficiency is increased. Examples of hydrophilic vinyl monomers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc., as well as maleic anhydride which easily generates carboxylic acid upon contact with water / amine,
Examples thereof include itaconic anhydride and methacrylic anhydride, and one or more of these can be selected and used. Furthermore, in order to increase the polymerization rate,
Other non-hydrophilic vinyl monomers can be used as the copolymerization component. A method of neutralizing an unreacted carboxyl group with an amino compound, ammonia, an alkali metal, or the like is also used for a polyester having a hydrophilic site introduced by these acrylics.

As a method for producing the polyester, known methods can be used. For example, the above dicarboxylic acid and diol components are transesterified at 150 to 250 ° C., and then polycondensed at 230 to 300 ° C. under reduced pressure. Thereby, the desired polyester can be obtained.

The aqueous dispersion can be produced by a known method. For example, the aqueous dispersion may be dissolved in a high boiling organic solvent such as butyl cellosolve and then dispersed in water by adding hot water. After dissolving in methyl ethyl ketone, the mixture is dispersed with a mixed solution of isopropyl alcohol / water, and the organic solvent is distilled off, whereby a complete aqueous water dispersion can be obtained.

The hot melt adhesive used in the present invention is:
Any of various types can be used. In particular, when a polyethylene-based hot melt adhesive is used, when the water dispersion of the present invention contains 5 to 70% by weight, preferably 10 to 60% by weight, and more preferably 15 to 50% by weight of polyethylene powder, Strength can be increased.

The aqueous dispersion of the present invention can be adjusted to a viscosity and viscosity suitable for workability by using various thickeners. From the viewpoint of the stability of the system due to the addition of a thickener, nonionic compounds such as methylcellulose and polyalkylene glycol derivatives, and anionic compounds such as polyacrylates and alginates are preferred.

The aqueous dispersion of the present invention can further improve the applicability to fabric and permeation by using various surface tension modifiers. In order not to impair the adhesive strength, the addition to the resin should preferably be limited to 1 wt% or less, more preferably 0.5 wt% or less.

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The measured values described in the examples are measured by the following method.

Number average molecular weight: 0.03 g of a polyester resin was dissolved in 10 ml of tetrahydrofuran,
Permission Chromatograph
h.

Glass transition temperature, melting point: Measured with a DSC 220 model manufactured by Seiko Denshi Kogyo KK at a heating rate of 20 ° C./min. 5 mg of a measurement sample was placed in an aluminum pan, and the lid was pressed down to seal and measurement was performed.

Aqueous dispersion particle size: The aqueous dispersion was adjusted to a solid concentration of 0.1 wt% with ion-exchanged water, and measured at 20 ° C. with a laser light scattering particle size distribution analyzer Coulter model N4 (manufactured by Coulter).

A method for preparing a sample for measuring the adhesive strength will be described below. First, the water dispersion is applied to a nylon interlining in the form of dots on a screen having 18 dots per inch.
After applying g / m ² (dry weight), the resin was sprinkled with a polyamide resin to sufficiently remove the non-polyamide adhered to the dots, and then temporarily attached in an oven at 150 ° C. for 1 minute.
Overlay the polyester / wool outer material on the adhesive interlining,
15 seconds at 130 ° C using Asahi press machine JR600,
Bonding was performed at a gauge pressure of 29 kPa. At this time, the total weight of the aqueous dispersion and the polyamide was adjusted to 5 g / m ² . After storing the obtained sample at room temperature for 24 hours,
The adhesive strength was measured.

Cleaning: The test method is JIS. L. 1
086. For dry cleaning, the value after three tests is described. In the warm water test, warm water at 40 ° C. and 60 ° C. was used at the time of washing. This also shows the value after three tests.

Example 1 Preparation Example of Polyester 83 parts by weight of terephthalic acid, 79 parts by weight of isophthalic acid, 5-part weight of 5-phthalic acid were placed in a reaction vessel equipped with a stirrer, a thermometer and a condenser for distilling.
Na sulfoisophthalic acid 7 parts by weight, ethylene glycol 74 parts by weight, neopentyl glycol 83 parts by weight, tetrabutyl titanate 0.068 parts by weight,
The esterification reaction was performed at 220 ° C. for 2 hours. After the completion of the esterification reaction, the temperature of the reaction system was raised from 220 ° C. to 255 ° C., while the inside of the system was gradually reduced in pressure, and the pressure was increased to 5 Torr at 255 ° C. over 60 minutes. And one more Torr
Polycondensation reaction was performed for 30 minutes below to obtain polyester (I). As a result of NMR analysis of the polyester (I), the dicarboxylic acid component contained 50 mol% of terephthalic acid and 47% of isophthalic acid.
Mol%, 5-Na sulfoisophthalic acid 3 mol%, and the diol component had a composition of ethylene glycol 50 mol% and neopentyl glycol 50 mol%. (Sulfonic acid group concentration: 139 equivalents / 10 ⁶ g)

Production Example of Aqueous Dispersion In a reaction vessel equipped with a stirrer, thermometer and reflux condenser, 34 parts of polyester (I) and 11 parts of n-butyl cellosolve were added.
The mixture was dissolved at about 80 ° C, and then stirred at 80 ° C with warm water 5
5 parts were added and dispersed in water. After cooling to room temperature, 0.1 part of Surfynol 104PA (manufactured by Nissin Chemical Co., Ltd.) and 0.85 part of Rheogic 305H (manufactured by Nippon Pure Chemical) were added and stirred sufficiently to obtain an aqueous dispersion (I). .

Example 2 Production Example of Polyester In the same manner as in Example 1, 80 parts by weight of terephthalic acid, 80 parts by weight of isophthalic acid, 5-Na sulfoisophthalic acid 1
1 part by weight, 112 parts by weight of ethylene glycol, 21 parts by weight of diethylene glycol, 0.1 part of tetrabutyl titanate.
Polyester (II) was obtained using 068 parts by weight as a raw material. As a result of NMR analysis of the polyester (II), the dicarboxylic acid component contained 48 mol% of terephthalic acid and 48 mole% of isophthalic acid.
Mol%, 5-Na sulfoisophthalic acid 4 mol%, and the diol component had a composition of ethylene glycol 80 mol% and diethylene glycol 20 mol%. (Sulfone base concentration: 195 equivalent / 10 ⁶ g)

Production Example of Aqueous Dispersion 100 parts of polyester (II) and methyl ethyl ketone 12 were placed in a reaction vessel equipped with a stirrer, thermometer and reflux condenser.
After dissolving 0 parts at about 80 ° C., a mixed liquid of 30 parts of isopropyl alcohol and 240 parts of water was added and dispersed in water with stirring. Thereafter, a condenser for distilling was provided, and after evaporating the solvent, the mixture was cooled to room temperature, and 0.3 parts of Surfynol 104PA (manufactured by Nissin Chemical Industry) and 2.5 parts of Rheogic 305H (manufactured by Nippon Pure Chemical) were added. And the mixture is sufficiently stirred to obtain an aqueous dispersion (II).
I got

Example 3 Production Example of Polyester 83 parts by weight of terephthalic acid, 83 parts by weight of isophthalic acid, 74 parts by weight of ethylene glycol, neopentyl glycol 8 were placed in a reaction vessel equipped with a stirrer, a thermometer and a condenser for distilling.
3 parts by weight and 0.068 parts by weight of tetrabutyl titanate were added, and an esterification reaction was performed at 170 to 220 ° C. for 2 hours. After the completion of the esterification reaction, the reaction system was heated from 220 ° C. to 25 ° C.
While the temperature was raised to 5 ° C., the pressure inside the system was gradually reduced, and the temperature was raised to 255 ° C. and 5 Torr over 60 minutes. After a polycondensation reaction is further performed at 1 Torr or less for 10 minutes, the mixture is cooled to 230 ° C. under a nitrogen atmosphere, 7 parts of trimellitic anhydride is added, and the mixture is stirred for 30 minutes to obtain polyester (II).
I) was obtained. Polyester (III) has an acid value of 35
It was 0 equivalent / 10 ⁶ g.

Production Example of Aqueous Dispersion 100 parts of polyester (III) and methyl ethyl ketone 1 were placed in a reaction vessel equipped with a stirrer, thermometer and reflux condenser.
A mixture of 20 parts and 30 parts of n-butyl cellosolve was added and dissolved at about 80 ° C.
0 parts, 3 parts of N, N-dimethylaminoethanol,
Under stirring, 230 parts of 80 ° C. warm water was added and dispersed in water. Thereafter, a condenser for distilling was provided, and after distilling off methyl ethyl ketone isopropyl alcohol, the mixture was cooled to room temperature. 0.5 parts was added and sufficiently stirred to obtain an aqueous dispersion (III).

Comparative Example 1 Production Example of Polyester 83 parts by weight of terephthalic acid, 83 parts by weight of isophthalic acid, 74 parts by weight of ethylene glycol, neopentyl glycol 8 were placed in a reaction vessel equipped with a stirrer, a thermometer and a condenser for distilling.
3 parts by weight and 0.068 parts by weight of tetrabutyl titanate were added, and an esterification reaction was performed at 170 to 220 ° C. for 2 hours. After the completion of the esterification reaction, the reaction system was heated from 220 ° C. to 25 ° C.
While the temperature was raised to 5 ° C., the pressure inside the system was gradually reduced, and the temperature was raised to 255 ° C. and 5 Torr over 60 minutes. Then, a polycondensation reaction was further performed at 1 Torr or less for 30 minutes to obtain a polyester (IV). Polyester (IV) is NMR
As a result of analysis, the dicarboxylic acid component had a composition of 50 mol% of terephthalic acid and 50 mol% of isophthalic acid, and the diol component had a composition of 50 mol% of ethylene glycol and 50 mol% of neopentyl glycol.

Production Example of Aqueous Dispersion 30 parts of polyester (IV) was
Pulverize to 50μ, add 70 parts of water, add 0.1 parts of Surfynol 104PA (manufactured by Nissin Chemical Co., Ltd.) and 0.85 parts of Rheogic 305H (manufactured by Nippon Pure Chemical Industries) and stir well. A dispersion (IV) was obtained.

Table 1 shows the characteristics of the aqueous dispersion, the adhesive strength, the strength after dry cleaning and the strength after hot water cleaning.

[0043]

[Table 1]

[0044]

As described above, according to the present invention, there is provided an adhesive for an adhesive interlining having excellent adhesive strength to various base cloths, especially polyester cloth, and having a small decrease in adhesive strength during hot water cleaning and dry cleaning. it can.

Claims (6)

[Claims] 1. An adhesive for an adhesive interlining, which is an aqueous dispersion of a polyester resin composition having a polar group in a molecule. 2. The adhesive according to claim 1, wherein the polar group of the polyester resin and the concentration thereof are (A) and / or (B) below. (A) 50 to 500 equivalents / 10 ⁶ g of sulfonate group (B) 200 equivalents / 10 ⁶ g or more of carboxyl group 3. The adhesive according to claim 1, wherein the polycarboxylic acid component of the polyester resin comprises 40 to 100 mol% of an aromatic dicarboxylic acid. 4. A polyester resin having a glass transition temperature of 20.
The adhesive agent for an adhesive interlining according to any one of claims 1 to 3, wherein the adhesive temperature is at least 0C. 5. A polyester resin having a number average molecular weight of 700.
The adhesive for an adhesive interlining according to claim 1, wherein the adhesive is 0 or more. 6. The adhesive according to claim 1, wherein the particle size of the aqueous dispersion particles is 1 μm or less.