JPS58219005A - Method of impregnating treating liquid - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for impregnating various objects to be treated with a treatment liquid in a short time.

When processing objects such as vegetable fibers such as cotton and hemp, animal fibers such as wool and silk, and wood using a processing solution such as a bleaching solution or a dyeing solution, ■ place the objects in the processing solution. The treatment liquid can be applied to the workpiece by immersing it in water, ■ applying the treatment liquid to the surface of the workpiece, or ■ placing the workpiece in a tank and reducing the pressure, and then injecting the treatment liquid into the tank. Impregnation is performed. However, in the above immersion method, in order to impregnate the processing liquid to the internal diameter of the object to be processed,
There are disadvantages in that it is necessary to boil the object to be treated for a long time while immersed in the treatment liquid, which takes a long time for impregnation, and a large amount of treatment waste liquid is produced, which requires a large amount of cost for its treatment. Although the coating method (2) is easy to work with, it has the disadvantage that the processing liquid cannot be impregnated into the inside of the object to be processed. With the reduced pressure method (2), it is possible to impregnate the inside of the object with the processing liquid, but it requires large-scale equipment, complicates the work, and increases the cost of impregnation. There is a drawback that processing waste liquid is also produced.

This invention has been made in view of the above circumstances, and is a book whose gist is a method of impregnating a processing liquid, which is characterized by applying dielectric heating prior to impregnating the object to be processed with the processing liquid.

That is, in the present invention, the object to be treated is dielectrically heated prior to impregnation, so that the object to be treated becomes susceptible to temporary or permanent trap impregnation. Therefore, the treatment liquid can be impregnated in a short time without causing the above-mentioned problems. For example, fibrous materials such as cotton, hemp, and wood,
Microscopically, it consists of a crystalline region in which structural units such as cellulose are regularly arranged and an amorphous region in which the arrangement of cellulose and other substances is disordered and there are pores containing gas, moisture, etc. When applied, the amorphous region where pores are present increases, and the substance is heated from the inside, moisture evaporates from the inside, and diffuses to the outside with air and gas inside. In this state, when the processing liquid is brought into contact with the object to be processed, the object to be processed is cooled and the inside is brought into a reduced pressure state. The degree of this depressurization is as large as the interior core. Therefore, the processing liquid quickly penetrates into the center of the object to be processed.
Impregnation with the treatment liquid can be accomplished in a short time. This effect, combined with the effect of increasing the number of amorphous regions with many pores, allows the impregnation of the treatment liquid to be carried out in an extremely short time.

Next, this invention will be explained in detail.

Various types of books can be cited as the objects to be processed according to the present invention. Examples include vegetable fibers such as cotton and hemp, animal fibers such as wool and silk, regenerated cellulose fibers, amino fibers, other synthetic fibers, wood, paper, pulp, wood flour/chips, and leather. The shape of the object to be processed is not limited in any way.

Further, the object to be treated may be pretreated by washing with hot water, washing, etc.

The dielectric heating is performed by irradiating the object with microwaves or high frequency waves. Generally, microwaves have a frequency of 3X108 to 3X10"H.

High frequency has a frequency of 3X108 to 3X10
7H7. In this invention, any book in this wavelength range can be used freely. Also, its output,
This book does not limit the irradiation time, etc. However, in Japan, according to the Radio Law, microwaves are limited to 2450 MH and 9 MHz.
Since the use of only two types of 15 MH is permitted, one must choose between these two types.

Note that a magnetron, a klystron, or the like is used as the microwave irradiation device, and a high frequency oscillation tube or the like is used as the high frequency irradiation device.

As the treatment liquid, one depending on the content of the treatment to be applied to the object to be treated is used as appropriate. For example, dyeing liquid, bleaching liquid, resin liquid, textile processing liquid, preservative liquid.

Insect repellent liquid, leather tanning liquid, flame retardant liquid, waterproofing liquid.

An appropriate treatment liquid is used from moisture-proofing liquids, antistatic liquids, and the like. The conditions (temperature, concentration, viscosity, etc.) of such a treatment liquid are not limited in any way, and are appropriately determined depending on the content of the treatment. Moreover, the processing amount is also determined appropriately. Note that the method of impregnation with the treatment liquid is not limited at all. Dipping, coating, etc. are performed as appropriate.

In this invention, dielectric heating is applied to the object to be treated prior to impregnation with the treatment liquid. In this case, it is desirable to adjust the water content of the object to be treated so that dielectric heating can be performed effectively.

The preferred range of water content depending on the type of material to be treated is as follows.

Vegetable fibers such as cotton and hemp: 3 to 50 (weight, same below) Animal fibers such as wool and silk: 3 to 50 Regenerated cellulose fiber = 3 to 50 Thiamino fiber
: 3-50 Other synthetic fibers : 3-50
Wood: 8-130 Paper: 5-40 Wood flour/chip: 8-130 Cylindrical bark
: Sections 5 to 100 In this way, by applying dielectric heating prior to impregnation with the processing liquid, the object to be processed is in a state where it is easy to be impregnated, and the impregnation with the processing liquid in the subsequent work is completed in a significantly short time. become. That is, for example, in fibrous materials such as cotton, hemp, and wood, dielectric heating increases the amorphous region where pores exist, and moisture, air, etc. within the material are pushed to the outside. . When the processing liquid is brought into contact with the object to be processed in such a state, the object to be processed is cooled, water vapor condenses within the object, and a reduced pressure is created, allowing the processing liquid to quickly penetrate into the object. In dielectric heating, the object to be processed is heated from the inside, and the higher the temperature, the higher the temperature inside the object, so the degree of pressure reduction is also important, and the processing liquid quickly penetrates into the inside. On the other hand, in normal heat transfer radiation heating, heating is performed from the outside of the object to be processed, and the outside becomes hotter than the inside, so there is no internal depressurization like in dielectric heating, and the heating is carried out inside the processing liquid. Penetration becomes extremely slow and requires a long time for impregnation.

The method of the present invention includes a staining solution as described above as a treatment solution;
It is extremely effective when processing using a decolorizing solution or the like. Furthermore, remarkable effects can be obtained when applied to impregnation of a base material with a resin liquid during the production of a laminate. In other words, in order to improve the punching processability, solder heat resistance, and electrical performance of laminates in the manufacture of laminates, the impregnating resin liquid is modified with tung oil and the resin is made into polymers. The impregnating property of the resin liquid becomes extremely poor. Therefore, surfactants and organic solvents have been used to improve this problem, but as a result, the hygroscopicity of the resulting laminate decreases (due to the surfactant) and heat resistance decreases (due to the residual organic solvent). A phenomenon is occurring.

According to the method of the present invention, a substrate can be impregnated with a resin liquid using a modified resin or a polymer resin without using a surfactant or an organic solvent, so that remarkable effects can be achieved.

In addition, when using a dyeing liquid or a decolorizing liquid as the treatment liquid, after impregnating the dielectric heat-treated workpiece with the dyeing liquid or decolorizing liquid, the workpiece is placed in saturated steam and heated again. Riddles to promote staining and bleaching reactions. In particular, if this reheating is performed by dielectric heating, the dyeing reaction and decolorization/spreading will be further promoted.

As described above, the present invention dielectrically heats the object to be treated prior to impregnation with the treatment liquid, so that the treatment liquid can be rapidly impregnated into the inside of the object. Therefore, the impregnation time can be significantly shortened. In addition, dielectric heating makes it easier for the object to be impregnated, so instead of immersing the object in the processing solution as in the past, you can use only the required amount of processing solution. It becomes sufficient to supply the liquid by coating or the like, and it becomes possible to save processing liquid and completely eliminate processing waste liquid. Moreover, the dielectric heating device itself is not large-scale and does not complicate the work, so it does not increase the cost of impregnation or make impregnation difficult.

Next, examples will be explained together with comparative examples.

[Example 1] Agatis veneer for laminated decorative veneer (artificial precious wood) with moisture content of 10 to 20 (300 mm
mm t ) were stacked, placed in a shield container, and irradiated with microwaves at 2450 MH and 2 KW output for 4 minutes.

At this time, 100°C saturated steam was blown into the container. Next, apply H20 on both sides of the microwave irradiated veneer.
! 30I4 aqueous solution (pi(4)) with a roll coater.
It was applied at a rate of 0.01/m". Then, it was stacked and
The sample was placed in a container filled with steam at 00°C and left for 20 minutes. As a result, a bleached veneer whose entire surface was uniformly bleached was obtained. In this case, the required time was 20 to 30 minutes, which was a significant time reduction compared to the conventional example (required time of 3 to 4 hours).

[Example 2] NaOH was applied to both sides of Agatis veneer (300 mm x 300 mm x 2.
1 volume of aqueous solution 3 was applied at a rate of 15011/m2, and 40 sheets were stacked and placed on a rotary plate 5 in a shield container 4 as shown in Fig. 3, and rotated to prevent uneven irradiation. 2450 from the microwave irradiation device 6 while
Microwave was irradiated for 6 minutes at MHz and 2KW output.

At this time, the container 4 is heated to 100°C from the steam blowing pipe 7.
of saturated steam was blown into the tank. Next, take this out and as shown in Figure 4, apply heat on both sides with a sponge roll 8.
1 each of 30% aqueous solution (pH 4, room temperature) 9 of 0°
501/m'', stacked 40 sheets, placed on the rotary plate 5 in the shield container (Fig. 5) 4, and while rotating it to prevent uneven irradiation, the microwave irradiation device 6
Microwave was irradiated for 10 minutes at 2450 MHz and 2 KW output. Next, I defeated this. As a result, as shown in Figure 6, the bleached veneer (
Since the veneer was heated from inside, it was uniformly decolored to the inside.) No. 10 was obtained.

In this example, before decolorizing using Hoot, the veneer 1 is degreased by applying alkali, and H2 (h (usually acidified and stabilized) is applied in the subsequent process. ) is made alkaline to make it easier to decompose, and before decolorization, microwave irradiation promotes the penetration of H! The effect of decolorizing and tightening the vines was also obtained.

[Example 3] The microwave irradiation for pretreatment (Fig. 3) was set to the output IKW, and the microwave irradiation for decolorization was set to the output IKW 3.
It took a minute. Then, after microwave irradiation for decolorization,
Steam treatment was performed by placing the sample in a container filled with steam at 100° C. for 20 minutes.

As shown in (7), by decolorizing using both microwave irradiation and steam treatment, the core material and defective materials (with resin, discoloration, etc.) that are difficult to completely decolor were effectively decolorized. .

[Example 4] Labra veneer (300 mm x 300
50 mmX LOmm t ) l l are stacked as shown in FIG. 7, fixed with a fixing band 12, placed in a shield container 13 as shown in FIG. , irradiate with microwave for 4 minutes with an output of 2KW.9. At this time, 100° C. saturated steam was blown into the container 13 from the steam blowing pipe 15. Next, take it out and immediately add Na as shown in Figure 9.
It was immersed for 30 seconds in an aqueous solution of OH. Then,
This was placed in the above-mentioned shield container (Fig. 8) 13, and after microwave irradiation under the same conditions as above, a 309 g aqueous solution of H2O2 (pH 4, room temperature) 17 was prepared as shown in Fig. 10.
15 seconds, and as shown in Figure 11.
It was placed in a container 58 filled with steam at 00°C and left for 15 minutes. As a result, a bleached veneer (not shown) whose entire surface was uniformly bleached was obtained.

In this example, in addition to obtaining the same effect as in Example 2, microwave irradiation is performed before alkali treatment, which promotes the penetration of alkali and has the effect of more uniform decolorization to the inside of the veneer. Obtained.

[Example 5] Cotton cloth (300 x 300 x 0.3 mm, moisture content 51)
The 20 stacked sheets were placed in a microwave irradiation device with a frequency of 2450 MHz and an output of 5 KW, and irradiated with microwaves for 2 minutes.

Next, take it out and immediately apply an aqueous solution of 8102 010 at a rate of 30 p/m2, and then heat it at 100°C.
The cloth was left to stand for 15 minutes at medium pressure in saturated steam, and then dried with hot air to obtain a decolorized cotton cloth.

This bleached cotton cloth was uniformly and sufficiently bleached throughout.

[Example 6] Rotary veneer of agathis for laminated decorative material (thickness 1.0
mm, 150X150mm) After decolorizing 50 sheets with hydrogen peroxide solution, 2450MHz, output 500W
The sample was placed in a microwave oven using 1 microwave and irradiated with 1 microwave for 3 minutes. 1. Remove this veneer and immediately apply a commercially available acid dye (C, I Ac1d Brow 13).
11 aqueous solution was applied so that the dye adhesion amount was 1.51/m''.Next, this was irradiated with microwaves of 2450 MHz and output of 500 W for 3 minutes in saturated steam to obtain a dyed veneer. .

After drying the resulting dyed veneer, we scraped it down to half its thickness and examined the internal color, which revealed that it was very uniformly dyed.

[Example 7] Rapla rotary veneer (thickness 1.0 mm, 15
After pre-rinsing 50 sheets (0x150mm) with hot water of IOO'C, 2450MHz, output 500. The sample was placed in a microwave oven using a W microwave and irradiated with microwaves for 2 minutes. Next, take out this veneer and immediately dye it with a commercially available direct dye (C, I Direct Yellow 50).
A 1-ti aqueous solution of was applied so that the dye adhesion amount was 2.01/-. Next, add 2450MHz to this, output 60
A dyed veneer was obtained by irradiating with 0W microwave for 2 minutes.

After drying the resulting dyed veneer, we scraped it down to half its thickness and examined the internal color, which revealed that it was very uniformly dyed.

[Example 8] Aius rotary veneer (thickness 1.0 mm).

50 sheets (150×15 Gmm) were treated in the same manner as in Example 2 and coated with dye. Next, add 2450MHz to this
.

It was irradiated with microwaves with an output of 600 W for 1.5 minutes, and further heated in saturated steam for 10 minutes to obtain a dyed veneer.
・After drying the obtained dyed veneer, we shaved it down to half its thickness and examined the internal color, which revealed that it was very even [Comparative Example 1] Labra rotary veneer (thickness 1.0 mm, 15
0X 150rrLn) was mixed with a commercially available acid dye (CI
Ac1d Br.

9 at a bath ratio of 40 in a dye bath of whB) of 0.4
When immersed at 5±2°C, the dyed veneer after 2 hours of immersion was uniformly dyed to the inside. However, books after immersing for 1 hour, books after immersing for 30 minutes, and books after immersing for 10 minutes,
The interior of the book was not fully stained.

[Example 9] Rotary veneer of agathis for laminated decorative material (thickness 1.0
mm, 600x600mm) After decolorizing 50 sheets with hydrogen peroxide solution, this (moisture content 60I4) was
It was placed in a microwave irradiation device with a frequency of 50 MHz and an output of SKY, and was irradiated with microwaves for 4 minutes. Next, take out this veneer and immediately dye it with a commercially available acid dye (C, lAc1d Brow).
h 13 )' 11 aqueous solution at a coating amount of 1001/m
This dye solution coated veneer was heated to 100℃.
A dyed veneer was obtained by leaving it in saturated steam for 1 hour.

After drying the resulting dyed veneer, we shaved it down to half its thickness and examined the internal color, which revealed that it was very uniformly dyed.

[Example 10] Agatis rotary veneer (thickness 1
．． 0 mm, 300 x 300 mm) on a rotary plate 5 in a shield container 4 as shown in Fig. 43, and while rotating it to prevent uneven irradiation, microwave irradiation equipment 6
Microwave was irradiated for 4 minutes at 2450 MHz and 2 KW output. Next, take this out and cover both sides with a 30% aqueous solution of H2O2 (1 liter of NaOH is added to make the solution alkaline and facilitate the decomposition of H2O2) using a pair of upper and lower sponge rolls 8 as shown in Fig. 4. 1501/m
2, and stack 100 sheets of this to make 100 sheets.
It was left to stand in saturated steam at ℃ for 1 hour to decolorize it. The resulting decolorized veneer was then irradiated with microwaves for 4 minutes at an output of 3 KW in the same manner as above. Next, take it out and immediately dye it with a commercially available direct dye (0.1 Direct Ye
50) was applied at 1501/m'' in the same manner as the application of the H2O2 aqueous solution above, and heated at 100°C.
A dyed veneer was obtained by leaving it in saturated steam for 1 hour.

After drying the resulting dyed veneer, we scraped it down to half its thickness and examined the internal color, which revealed that it was very uniformly dyed.

[Example 11] Cardboard for film-retaining boxes (kraft paper, moisture content 8, thickness 3 mm)
, 300X300mm) 10 pieces at 2450MHz.

Put the microwave in a microwave irradiation device with an output of 3KW and turn on the microwave for 2 seconds.
Irradiated for minutes. Next, this was taken out and immediately coated with silicone oil at a rate of 1501/m'' and dried with hot air at 80°C to obtain waterproof cardboard.

When the water repellency of the obtained waterproof cardboard was examined, water repellency was observed up to the center of the interior of the cardboard.

[Example 12] Cedar board for outer fence obtained from small-diameter lumber (thickness 15 mm).

35X400myrx), 2450MHz, output 1
It was placed in a 0KW microwave irradiation device and irradiated with microwaves for 4 minutes. Next, this was taken out and immediately immersed in a commercially available naphthalene insect repellent solution for 30 seconds.

Then, it was dried at room temperature to obtain an insect-proofed cedar board.

When the resulting insect-repellent treated cedar board was cut, it was found that the inside center of the cedar board was impregnated with the insect repellent.

[Example 13] A common base paper for laminated products was subjected to humidity control treatment so that the moisture content was about 30% based on the total dry weight.

Next, this was fed into the microwave irradiation device at a rate such that the residence time in the microwave irradiation device was 1 minute, and microwave irradiation was performed. Then, the impregnating resin liquid was applied to both sides of the base paper at the outlet of the microwave irradiation device. Here, the impregnating resin liquid contains 1 phenol and 1 formaldehyde.
:1.30 molar ratio and reacted under reflux conditions for 3 hours under an ammonia catalyst to form a resin], to which about 10'l of methanol was added. Next, the base paper impregnated with the impregnating resin liquid is dried in a hot air dryer using a suitable Glynis (
It was dried until the amount of oozing was reached. The books thus obtained were laminated in accordance with a conventional method, and heated and pressurized in a press to harden the impregnated resin to obtain a laminated product.

The results of the performance test of the obtained laminate were good as shown in the table below.

[Examples 14 to 17] The following resin solution for impregnation was used in place of the resin solution for impregnation used in Example 1. A laminate was obtained in the same manner as in Example 1 except for the above.

The results of the performance tests of the obtained laminates were all extremely good as shown in the table below.

(Resin liquid for impregnation) Example 14! A resin liquid made by reacting phenol and tung oil under a para-toluenesulfonic acid catalyst, then adding metacresol and formaldehyde and reacting under a triethanolamine catalyst.

Example 158 Molecular weight 2000-3000. A resin liquid made by dissolving a bisphenol A type resin having an epoxy equivalent of 1000 to 2000, m-phenylenediamine, and a curing accelerator in MEK (ster ethyl ketone).

Example 16: A resin liquid prepared by dissolving a resin having a molecular weight of 1000 to 1500 and an epoxy equivalent of 500 to 100G, polyvinylphenol, and hardening accelerator [11t MEK.

Example 17: -Resin liquid prepared by blending diallyl heptatarate with a polyester resin consisting of robylene glycol, maleic acid, and isophthalic acid, adding and dissolving MEK, and further adding benzoyl peroxide.

[Comparative Examples 2 to 6] Comparative Examples 2 to 6 correspond to Examples 13 to 17, respectively, and laminates were prepared using the same impregnating resin liquid as used in Examples 13 to 17 in the following manner. Manufactured. That is, a resin liquid for impregnation is placed in a dip pan, and a base paper for ordinary laminated products is immersed in the resin liquid without being irradiated with microwaves, and the resulting base paper impregnated with the resin liquid is processed. Laminated products were produced in the same manner as in Examples 13 to 17.

As shown in the table below, the performance test results of the obtained laminate were considerably inferior to those of the example products.

(Hereafter, extra white)

[Brief explanation of the drawing]

Figures 1 to 5 are explanatory diagrams of one embodiment of the present invention, Figure 6 is a perspective view of a bleached veneer obtained thereby, and Figures 7 to 411 are explanatory diagrams of other embodiments. It is. l...Agathis veneer 2...Sponge roll 3...
・NaOH aqueous solution 4... Shield container 5... Rotating plate 6... Microwave irradiation device 9... H,02
Aqueous solution lO... Decolorization Veneer Patent Applicant Matsushita Electric Works Co., Ltd. Agent Patent Attorney Takehiko Matsuki Figure 2 6 Figure 4 Figure 7 4 Figure 10 Figure 11

Claims (3)

[Claims] (1) A treatment liquid impregnation method characterized by applying dielectric heating to the object to be treated prior to impregnating the treatment liquid with the treatment liquid. (2) A patent in which the treated material is selected from the group consisting of plant fibers, animal fibers, regenerated cellulose fibers, amino fibers, other synthetic fibers, wood 1 paper, pulp, wood flour, chips, and leather. A method for impregnating a treatment liquid according to claim 1. (3) The processing liquid is a dyeing liquid, a bleaching liquid, a resin liquid, a textile processing liquid, an antiseptic liquid, an anti-corrosion liquid, a leather tanning liquid, a flame retardant liquid, a waterproofing liquid, a moisture-proofing liquid, and an antistatic liquid. A method for impregnating a treatment liquid according to claim 1 or 2, wherein the treatment liquid is selected from the group consisting of: (Ship) The treatment liquid impregnation method according to any one of claims 1 to 3, wherein the dielectric heating is performed using microwaves or high frequency waves.