JPS6155270A - Production of adhesive cloth - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method of manufacturing adhesive fabric. More specifically, after melting and bonding cloth using an ionizing radiation-curable resin as an adhesive, ionizing radiation is irradiated.
This relates to a method for producing an adhesive cloth characterized by making the adhesive layer three-dimensional and curing it to improve the adhesion, heat resistance, solvent resistance, water resistance, etc. of the adhesive area. Technology] In recent years, hot melt adhesives have been used in the field of bonding fabrics, particularly in the field of adhesive interlining. This is due to the fact that hot melt adhesives have a fast adhesion speed in the absence of solvents, exhibit strong adhesive strength instantly after cooling, and can also be used to shorten the sewing process. ), it takes advantage of the fact that the finish of the product can also be made uniform.

Conventionally, hot melt adhesives such as those listed below have been used in this field. First, the hot melt adhesives mentioned are nylon adhesives that have excellent dry cleaning resistance, and polynisdel adhesives that have excellent hot water wash resistance. Next, examples of reactive adhesives include reactive hot melt adhesives containing epoxy groups, incyanato groups, or active silyl groups. Conventionally, cloth has been bonded by thermocompression bonding using a hot melt adhesive as described above.

[Problem that the invention seeks to solve]

Adhesives conventionally used for bonding cloth have the following problems. In other words, currently commercially available hot melt adhesives for textiles do not necessarily satisfy heat resistance, water resistance, solvent resistance, etc., and nylon adhesives have excellent dry cleaning resistance, but are resistant to hot water. Polyester adhesives have a problem of poor washability, although they are excellent in hot water washing resistance, but have poor dry cleaning resistance.

Reactive adhesives have been developed to solve these problems, but adhesives have satisfactory performance in terms of suitability as a textile adhesive, heat resistance, water resistance, and solvent resistance. has not been obtained. That is, as a reactive adhesive, an instant adhesive such as α-cyanoacrylate,
Anaerobic adhesives such as dimethacrylate are well known, but these are liquid at room temperature (1), and when used for textiles, K oozes out during application, making them unsuitable for textile applications. . As a hot melt adhesive for textiles, it is desirable to use one that is solid at room temperature, but if you try to incorporate a double bond into a polyester or nylon adhesive resin and cause it to undergo a three-dimensional reaction using a radical initiator, The adhesive must be of a two-component type, which is inconvenient for bonding work. In addition, reactive adhesives that support reactive incyanate groups and activated silyl groups have been developed, but these types of adhesives are extremely unstable to moisture in the air647 and lack storage stability. ing. Furthermore, adhesives containing epoxy groups, which are reactive functional groups, have been developed.
If this is used, the adhesive must be of a two-component type, causing inconvenience in the bonding work.

As described above, in the field of bonding fiber materials using adhesives, many problems remain to be solved regarding the adhesives used.

If a reactive hot melt adhesive is to be used for bonding fibers, the adhesive must satisfy the following conditions (υ~(lv)).

(1) Demonstrate adhesive strength that can be handled within a short time after bonding.

(If) No longer exhibits thermal fluidity after curing.

This paper attempts to solve the above-mentioned problems by using it as an adhesive for cloth.

Means for Solving Problem C] Regarding the above problems, in particular, conventionally used adhesives have poor suitability as adhesives for textiles, heat resistance, water resistance, solvent resistance,
In order to solve the problem that hot water washing resistance and dry cleaning resistance are not necessarily satisfactory, in the present invention, an E-release radiation-curable polymer composition is used as an adhesive for fibers. Adopted.

In addition, methods for curing adhesives include a method of curing the resin by irradiating the adhesive with ultraviolet rays, and a method of curing the resin by irradiating the adhesive with ionizing radiation. If a curing method is used, the adhesive fabric that is the object of the present invention cannot be effectively produced. This is because when a thick resin layer is irradiated with ultraviolet rays, only the surface layer of the resin is cured by the ultraviolet rays, and the curing reaction does not extend to the inside of the resin. By using the curable polymer composition as an adhesive, it is possible to effectively produce the adhesive fabric that is the object of the present invention.

That is, the present invention involves placing or adhering an ionizing radiation-curable polymer composition on a cloth or knit product, and then overlaying the same or different cloth or knit product on top of the ionizing radiation-curable polymer composition. The present invention provides a method for producing an adhesive fabric, which comprises bonding and then curing the polymer composition by irradiating with ionizing radiation.

The ionizing radiation-curable polymer of the present invention is stable in the presence or absence of a polymerization inhibitor as long as ionizing radiation or a polymerization initiator is not added, has good storage stability, and has a good shelf life after bonding. When irradiated with ionizing radiation, it becomes three-dimensional in a short time, loses thermal fluidity, and has excellent adhesive properties, #f solvent resistance, water resistance, heat resistance, and dry cleaning resistance.

urethane (meth)acrylate, polyether (meth)acrylate, polyepoxy (meth)acrylate,
The main components are polymers that undergo a crosslinking reaction when exposed to ionizing radiation, such as polyacrylamide, polyvinyl 44ide, polyamide, (unsaturated) bolyer, (unsaturated) polyether, polysiloxane, and polyacrolein. '
There is C. These polymers can be used alone or in the form of a mixture or copolymer of two or more rings. Considering that adhesives for fibers should preferably have a fast curing speed and require a small amount of curing radiation, it is preferable to use polymers in which the terminal or side chain of the main chain is acrylic-modified. It is not limited to this. Examples of acrylic modified polymers include polyester (meth)acrylate,
Examples include polyurethane (meth)acrylate, polyether (meth)acrylate, polyepoxy (meth)acrylate, etc. Among them, considering adhesiveness, flexibility, and solvent resistance, polyester (meth)acrylate and polyurethane (meth)acrylate are used. Most preferably, acrylates are used.

The method for synthesizing polyester (meth)acrylate and polyurethane (meth)acrylate is not particularly limited, and known methods can be used. For example, polyester (meth)acrylate is synthesized as follows. A prepolymer polyester having a dicarboxylic acid and a human cI sil group at the opposite end of the acid is obtained. By reacting this with (meth)acrylic acid, a polyester containing (meth)acryloyl groups (
Obtain meta)acrylate.

Although various resins can be used as a prepolymer for polyurethane (meth)acrylate, it is most preferable to use polyester or polyether as a prepolymer. When using polyester as a prepolymer, the same prepolymer polyester used in synthesizing the above-mentioned polyester (meth)acrylate can be used. For example, this prepolymer polyester and 2
-Polyurethane (meth)acrylate is obtained by reacting hydroxyethyl (meth)acrylate with tolylene diisocyanate. When a polyether is used as a prepolymer, it may contain a polyurethane double bond by reacting poly(alkylene oxide) glycol, polyfunctional isocyanate, or 2-hydroxy(meth)acrylate, and a carboxylic acid component may be added. In some cases, unsaturated dicarboxylic acids such as maleic acid and fumaric acid are included. However, if the amount of unsaturated dicarboxylic acid introduced is too large, the flexibility after curing is lost, making it undesirable for use as a hard and brittle resin or as an adhesive for fibers.

Therefore, the amount of unsaturated dicarboxylic acid introduced is preferably 70% or less of the total amount of carboxylic acid introduced.

The ionizing radiation curable polymer composition obtained using the above components has a number average molecular weight of 1000 to tooooo and a softening point of 60 to 170C. Also, 2 from the softening point
Melt viscosity at 0C high temperature is 3000~5 G OOD
0 ape.

A composition having such physical properties is suitable as an adhesive for fibers.

The polymer composition used in the present invention does not lose its hot melt properties! i! In B, it is also possible to contain an unsaturated supermer as a reactive diluent, if necessary. . Preferred unsaturated monomers as reactive diluents include, for example, styrenic unsaturated monomers and acrylic unsaturated monomers.

It is also possible to add additives such as. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether, t-butylhydroquinone, 2,5-di-t
-butylhydroquinone, 2-methylhydroquinone 7, etc., and it is preferable to use them in a range of 0.001 to 1.0% by weight.

The method for placing or adhering the ionizing radiation-curable polymer composition used in the present invention on cloth is not particularly limited, and known methods can be used. When applying in a molten state, existing hot melt applicators and hot melt coaters can be used. In addition, when applying in powder form, powder coating method, dot coating method, antistatic coating method, heat-sensitive coating method, etc. can be used, and the difference in these shapes is caused by ionizing radiation. Although it does not affect the curing effect, when using a film or net form, the adhesive layer should be 0.51
It is desirable that it be 1Ia+ or less. Adhesive layer is 0,5
(2) If the adhesive is more than that, the texture after adhesion becomes poor, the transmittance of ionizing radiation is poor, and high energy is required.

The melt adhesion method is not particularly limited, and any known method such as heat press adhesion, infrared heat adhesion, ultrasonic adhesion, and other high frequency energy adhesion methods can be used.

The adhesive fabric K thus obtained is irradiated with ionizing radiation to make the adhesive three-dimensional. As ionizing radiation,
Examples include α-rays, β-rays, r-rays, X-rays, and electron beams, but in consideration of high processing speed, cost reduction, etc., it is most preferable to use electron beams. Further, if necessary, melt bonding and ionizing radiation irradiation can be performed simultaneously.

In the present invention, both high-voltage spot beam scanning type and electron curtain type electron beam accelerators can be used. The electron beam irradiated from such an accelerator is preferably one having an energy of 100''-500K6v't-0, with an irradiation dose in the range of 1 to 50 Mrad, and more preferably an irradiation dose in the range of Q, 1 to 50 Mrad. 2°Mrad.Irradiation time is 0.1
~30 seconds is preferred.

[Effect]

The ionizing radiation-curable polymer obtained as described above has a number average molecular weight of 1,000 to 100,000 and a softening point of 60 to 170 tll'. The melt viscosity at a temperature 20C higher than the softening point is 3,000 to 3,000,000 ps. A polymer composition having such physical properties acts suitably as an adhesive for fibers. That is, the cloth does not need to be heated in the oven during bonding, and the adhesive can be prevented from seeping onto the back surface of the cloth. If the softening point is higher than 17DC, a higher temperature is required when hot-melt bonding the fabric, which may cause damage to the fabric.

Also, the melt viscosity at a temperature 20C higher than the softening point is 3000
In the case of cps and JS, oozing to the back side of the fabric is observed, which is unfavorable in appearance, and furthermore, an anchor effect to the fabric cannot be expected, resulting in poor adhesion.

In the present invention, 100 to 50
Irradiation with an electron beam with an energy of 0 KeV @ fl
0.1-50 Mrad, preferably 0.1-20
Used at doses in the range of Mrad. Such an electron beam can cure the ionizing radiation-curable polymer composition of the present invention to a suitable state. If the irradiation dose is too small, the formation of crosslinks in the polymer composition may be insufficient, resulting in poor adhesion,
Improvements in heat resistance, solvent resistance, etc. cannot be expected. In addition, if the electron beam irradiation dose is greater than 20 Mrad, the polymer Kurihashi density will be large, and it will lack flexibility, which is a desirable property as a general purpose adhesive, and the properties of the fabric itself will change. It may be the cause.

〔Example〕

Hereinafter, the present BA will be specifically explained using examples.
The present invention is not limited to these examples.

In the examples, "part" refers to the cut-off part, ethylene glycol 6
To 2 parts, 0.5 parts of di-n-butyltin oxide as an esterification catalyst and 0.2 parts of 2-methyl hydride as a polymerization inhibitor were added and reacted to form a hydrosil group at the terminal. A prepolymer polyester was synthesized (number average molecule '1fk620Q). 12 parts of acrylic acid and 20 parts of ethylene glycol were added to this, and polyester acrylate was synthesized by transesterification. The softening point of the obtained polyester acrylate was 92C as measured using the ring and ball method. Also, the melt viscosity at 110C is 120,000p! It was I. The polyester acrylate was molded into a sheet with a thickness of 50 μm, which was sandwiched between cloths and adhered by heat press. The fabric used was Tetron/cotton (65155) broad fabric.

The bonding conditions by heat press are: temperature: 130C, pressure: 2
00I/32, crimping time is 20 seconds.

In contrast to the adhesive fabric obtained in this manner, an adhesive fabric obtained by applying NHv Curetron (manufactured by Nissin High Voltage Co., Ltd.) was prepared. Dry cleaning tests on these cured adhesive fabrics.

After carrying out the washing test, the adhesive strength was measured. The results are shown in Table-1. The same test was also conducted on the adhesive cloth before electron beam irradiation, and a comparison was made between before and after electron beam irradiation.

Table 1 T-glow adhesive strength (1) 0 Test details As shown in Table 1, Km after irradiation and before irradiation. At the temperature T<) the test was carried out. The results are shown in Table 2.

As can be seen from Table 2, even when the temperature was raised to 70C, no change in adhesive strength was observed and an improvement in heat resistance was observed. Furthermore, the adhesive cloth after electron beam irradiation was placed in a constant temperature oven at 1300 °C and left for 24 hours under a pressure of 1 kt/self m2, but the adhesive cloth using any irradiation dose of 1.5.10 Mrad did not adhere No oozing of the agent was observed.

A powder synthesized in Example 1 with a hydroxyl group at the end and classified to have an average particle size of 120 μm was prepared. The softening point of the obtained polyurethane acrylate was 97C as measured using the ring and ball method. Moreover, the melt viscosity at 120C was 15,500 cps. The polyurethane acrylate powder was dot coated on a Tetron/cotton (65155) broad cloth at a coating amount of 15 f//m at 20 voids/t/Ql112, and the same powder was superimposed on top of the dots, and then heat pressed. The heat press bonding conditions were a temperature of 150C.

The pressure was 200 Imm2 and the crimping time was 20 seconds.

The thus obtained adhesive fabric was irradiated with an electron beam using NHV Curetron (Nissin High Voltage Co., Ltd. M) to obtain a cured adhesive fabric. Electron beam 1.6.10
An adhesive fabric obtained by irradiation with three doses of Mrad was prepared.

Next, the adhesive fabric was subjected to the same test as in Example 1, and the T-flake adhesive strength was measured. The results are shown in Table 3. Furthermore, a T peel test was conducted at the temperatures shown in Table 4. The results are shown in Table 4.

Table 3 T foil adhesive strength (3) Table 4 T foil adhesive strength (4) From Table 6.4, even when polyurethane acrylate is used, the electronic resistance is the same as when polyester acrylate is used. The curing effect due to the wire was observed in 8th place, and the adhesion, solvent resistance, water resistance, and heat resistance were improved. Also,
According to this example, the effect of electron beam curing is not affected by the application state of the adhesive, for example, the application shape;
It has excellent water resistance and heat resistance, and is flexible.
Can be used in many ways in adhesive sewing. Ifuri-e can be used to sew cuffs on short-sleeved shirts, sew hems on skirts, add names to fabrics, etc. It can also be used as an adhesive interlining, and the conventional problems such as rough texture and seepage of adhesive can be solved by the method of the present invention.

By using an electron beam curing method that can cure the adhesive in a short time, the adhesive processing speed can be significantly increased, which can greatly contribute to streamlining the sewing process. Furthermore, since energy can be intensively input to the target object, it is also effective in terms of energy saving.

Claims (1)

[Claims] 1. An ionizing radiation-curable polymer composition is placed or adhered to a cloth or knitted product, and then the same or different type of cloth or knitted product is superimposed on top of this and melt-bonded. . A method for producing an adhesive fabric, which comprises curing the polymer composition by subsequently irradiating it with ionizing radiation. 2. The method for producing an adhesive cloth according to claim 1, which uses an ionizing radiation-curable polymer composition having a number average molecular weight of 1,000 to 100,000. 3. Melt viscosity is 30 at a temperature 20℃ higher than the softening point.
2. The method for producing an adhesive fabric according to claim 1, using an ionizing radiation-curable polymer composition having an ionizing radiation curability of 00 to 300,000 cps. 4. The method for producing an adhesive cloth according to claim 1, wherein the ionizing radiation-curable polymer composition contains a reactive diluent.