JP2002127252A - Method for manufacturing laminated scrubbing brush - Google Patents

Abstract

PROBLEM TO BE SOLVED: To extremely reduce the curing time of an adhesive to rationalize the laminated scrubbing brush in a method for manufacturing the laminated scrubbing brush formed by laminating and bonding a nonwoven fabric and sponge through an adhesive. SOLUTION: A moisture curable polyurethane resin adhesive containing a polymeric compound having a polyoxyalkylene group in its molecular chain is applied to either surface of a nonwoven fabric. After water is sprayed on the adhesive surface, a sponge layer is laminated to this surface. High frequency heating is applied to this laminate and the moisture curable polyurethane resin adhesive is rapidly cured by high frequency heating. A polymeric compound having a polyoxyethylene group in its molecular chain is indispensably added to the moisture curable polyurethane resin adhesive. If this polymeric compound is not added, rapid curing cannot be realized. However, a polymeric compound having a polyoxypropylene group in its molecular chain or the like may be added to the moisture curable polyurethane resin adhesive along with this polymeric compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a laminated scourer in which a nonwoven fabric and a sponge are laminated and bonded, and uses a special adhesive which is easily adhered by high frequency heating as an adhesive for laminating and bonding. It is characterized by the following.

[0002]

2. Description of the Related Art Conventionally, a solvent-based moisture-curable polyurethane resin-based adhesive or the like has been used as an adhesive for laminating and bonding a laminated nonwoven fabric and a sponge. Since the solvent-type adhesive generally has a high initial tackiness, the adhesion between the nonwoven fabric and the sponge hardly decreases after the nonwoven fabric and the sponge are laminated via the adhesive. Therefore, after laminating the nonwoven fabric and the sponge,
Even if a long time is required for curing (curing by moisture), strong adhesion between the nonwoven fabric and the sponge can be realized. For this reason, solvent-based moisture-curable polyurethane resin-based adhesives have been widely used as adhesives for manufacturing laminated scourers.

However, when a solvent-type adhesive is used, the solvent is volatilized in the manufacturing process of the laminated scourer, and there is a problem from the viewpoint of working environment or safety. In addition, there is a problem that a solvent may remain in the adhesive layer or the like of the obtained laminated sashimi, giving a strange odor or discomfort to the consumer.

For this reason, it has been proposed to use a solventless moisture-curable polyurethane resin-based adhesive instead of the solvent-based adhesive. Solventless adhesives generally have low initial tack, so even if the nonwoven fabric and the sponge are laminated via this adhesive, the adhesion between the nonwoven fabric and the sponge will not be sufficient before the adhesive is cured. Sometimes it was enough.
That is, since the nonwoven fabric or sponge is rich in elasticity, the edge of the nonwoven fabric and the sponge do not adhere to each other, so that the sponge may be separated. Thus, while the adhesive cures,
For example, for several tens of minutes, the laminate of the nonwoven fabric and the sponge must be press-bonded, and there is a regret that the production of the laminated scourer cannot be performed rationally.

[0005]

Therefore, the present inventor has set forth
After laminating a nonwoven fabric and a sponge via a solventless moisture-curable polyurethane resin-based adhesive, an attempt was made to cure the adhesive by immediately applying high-frequency heating in the presence of moisture. Due to the presence of moisture and high-frequency heating,
This is because the adhesive was considered to be heated instantly and cured in a short time. However, even with such a method, it has been difficult to cure the adhesive in a satisfactory short time.

Further, the inventor of the present invention changed the kind of the solventless moisture-curable polyurethane resin-based adhesive in various ways and applied the above-mentioned high-frequency heating. Was found to cure in a very short time. The present invention is based on such a finding.

[0007]

That is, the present invention relates to a method for producing a sashimi piece A, wherein at least one surface of the sashimi piece A is provided with a moisture-curable polyurethane resin-based adhesive containing a polymer compound having a polyoxyethylene group in a molecular chain. After laminating the scrubbing pieces B different from the scrubbing pieces A, high-frequency heating is performed in the presence of moisture to cure the moisture-curable polyurethane resin-based adhesive, and the scrubbing pieces A and the scrubbing pieces B And a method for producing a laminated scourer, which is characterized in that:

First, in the present invention, a scrubbing piece A and a scrubbing piece B constituting a laminated scallops are prepared. As the scrubbing pieces A and B, those made of various conventionally known materials are prepared. As scrubbing pieces A and B, different types of scrubbing pieces are prepared. This is because the laminated scourer uses the scrubber piece A side or the scrubber piece B side depending on the type of the object to be cleaned, so that it is preferable that the types and materials of the two be different. For example, as the scrubbing pieces A, non-woven scrubbing pieces are prepared, and as the scrubbing pieces B, sponge scrubbing pieces are prepared.

On the other hand, a moisture-curable polyurethane resin-based adhesive containing a high molecular compound having a polyoxyethylene group in a molecular chain is prepared as an adhesive for bonding the scrubbing pieces A and B. The present invention uses a moisture-curable polyurethane resin-based adhesive containing this polymer compound,
It is characterized by high frequency heating. Examples of the high molecular compound having a polyoxyethylene group in the molecular chain include (i) polypropylene glycol such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol, and a compound having three active hydrogens added with a plurality of moles of propylene oxide. Polyoxypropylene triol, glycerin, trimethylolpropane, glucose, sorbitol, polyether polyol obtained by adding ethylene oxide to one or more polyhydric alcohols such as sucrose or polycondensation of polyethylene glycol, (Ii) glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, and a polymer compound obtained by reacting with polydiisocyanates such as diisocyanates; For example, a polymer compound obtained by reacting a dicarboxylic acid such as a meric acid or a hydrogenated dimer acid with a polyester polyol that is a polycondensate of polyoxyethylene glycol and a polyisocyanate such as a diisocyanate is used. . In particular, typically, polyoxypropylene triol obtained by adding a plurality of moles of propylene oxide to glycerin is reacted with polyoxypropylene polyoxyethylene triol obtained by adding 10 to 90 moles of ethylene oxide to polyisocyanates. It is preferable to use a polymer compound obtained or a polymer compound obtained by reacting polyoxypropylene polyoxyethylene glycol with a polyisocyanate and having an NCO group in a terminal group. Most preferably, a polymer compound obtained by reacting polyoxypropylene polyoxyethylene glycol obtained by adding 10 to 90 mol of ethylene oxide to both ends of polyoxypropylene glycol (or graft-polymerized with polyethylene glycol) and a diisocyanate And those having an NCO group in the terminal group are preferred. The reason for this is that if both terminal portions of the polymer compound are polyoxyethylene groups, they are cured in a short time. In addition,
The content of the terminal polyoxyethylene group in the polymer compound is preferably 5% by mass or more, and more preferably 30% by mass or more.

The moisture-curable polyurethane resin-based adhesive used in the present invention may be the above-mentioned polymer compound alone or may be a mixture with another substance. As the other substance, a polymer compound used as a conventionally known moisture-curable polyurethane resin-based adhesive can be used. For example, a polymer compound obtained by reacting a polyether polyol or polyester polyol having no polyoxyethylene group with a polyisocyanate is used. In particular, a polymer compound having a polyoxypropylene group in the molecular chain is used. Specifically, (i)
Polyether polyols obtained by adding propylene oxide to one or more polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, glucose, sorbitol, and soucrose; and polydiisocyanates such as diisocyanates Polymer compounds obtained by reacting
(Ii) Polyester polyol which is a polycondensate of dicarboxylic acid such as glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, hydrogenated dimer acid and polyoxypropylene glycol. And a polyisocyanate such as a diisocyanate. Typically, it is preferable to use a polymer compound obtained by reacting polyoxypropylene glycol with a diisocyanate and having an NCO group in a terminal group.

The above polyisocyanates include, for example, 2,4-tolylene diisocyanate, 2,2
6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate,
Aromatic polyisocyanates such as polymethylene polyphenylene polyisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicycles such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate and 4,4'-dicyclohexylmethane diisocyanate Formula polyisocyanates; aryl aliphatic polyisocyanates such as xylylene diisocyanate; and carbodiimide-modified or isocyanurate-modified polyisocyanates. These can be used alone or in combination of two or more. Among these, it is particularly preferable to use 4,4'-diphenylmethane diisocyanate.

As described above, the scallops A, the scrubs B and
Compounds having polyoxyethylene groups in the molecular chain
Prepared moisture-curable polyurethane resin adhesive containing
Then, on one side of the scrubbing piece A, this moisture-curable polyurethane
A resin-based adhesive is applied, and scrubbing pieces B are applied via the adhesive.
Are laminated. After lamination, high-frequency heating is applied.
However, at this time, if there is no moisture, the adhesive will not be heated.
No. Therefore, it is necessary to provide water by an appropriate method.
As a method of adding moisture, for example, before applying an adhesive
In addition, the method of keeping the water in the scrubbing pieces A, the adhesive
Method of applying moisture to the adhesive after application, scrubbing piece B
, A and B
After laminating and before high-frequency heating, water is applied to the laminate
An appropriate method such as a method for performing the above may be adopted. In addition, adhesion
The application amount of the agent is 50 to 250 g / m ^TwoDegree is preferred,
Especially 80 to 150 g / m^TwoThe degree is more preferred. adhesive
50 g / m^TwoIf it is less than the value, the adhesive strength is reduced.
There is a risk that. The amount of the adhesive applied is 250 g / m^Two
If it exceeds, the texture of the obtained laminated scourer tends to decrease.
Direction occurs. Furthermore, the amount of water to be applied is based on the adhesive mass.
Therefore, about 1/10 to 1/2 is preferable. In addition, high frequency
Heat can be achieved by using a well-known dielectric heating method.
The frequency to be used may be in a conventionally known range.

[0013]

Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the examples. The present invention should be interpreted as being based on the finding that if high-frequency heating is applied to a specific moisture-curable polyurethane resin-based adhesive, curing proceeds rapidly.

Example 1 A scallops piece A was 9 mm thick, 300 mm long and 30 mm wide.
A 0 mm nonwoven fabric was prepared. As a scallops B, thickness 5
A urethane sponge having a length of 4 mm, a length of 300 mm, and a width of 300 mm was prepared. Further, as a moisture-curable polyurethane resin-based adhesive containing a polymer compound having a polyoxyethylene group in a molecular chain, a polyoxypropylene glycol (average molecular weight = 600) obtained by addition polycondensation of ethylene oxide is used. Oxypropylene polyoxyethylene glycol (average molecular weight = 1500, polyoxypropylene group: polyoxyethylene group = 4: 6),
A polymer (hereinafter, referred to as "adhesive A") prepared by reacting 4,4'-diphenylmethane diisocyanate with a terminal NCO group content of 5% was prepared. .

Then, adhesive A was applied to one side of the nonwoven fabric using a roll spreader at an application amount of 200 g / m ² . Thereafter, 40 g of water was applied to the surface of the adhesive A layer.
/ M ² . Immediately thereafter, a urethane sponge was laminated on the surface of the adhesive A layer, and high-frequency heating was performed under the following conditions. [High-frequency heating conditions] High-frequency device: Air press type high-frequency heating device RH-7 manufactured by Yamamoto Vinita Oscillation frequency: 13.56 MHz Anode current: 0.9 A (high-frequency output 4.4 KW) Then, high-frequency heating is performed for a predetermined time. After that, the laminated scourer was taken out of the apparatus, and when the nonwoven fabric and the urethane sponge were peeled off by hand, it was confirmed whether or not the nonwoven fabric or the urethane sponge broke, and the curing time was evaluated. As a result, in the high-frequency heating for 10 seconds, the non-woven fabric or the urethane sponge was peeled off without breaking the material (in Table 1, the result is indicated by x). The sponge could not be peeled without rupture (in Table 1, this result was indicated by a circle). Therefore, by using the adhesive A, the curing time could be reduced to about 20 seconds. Note that E in Table 1
The O abundance indicates the abundance of oxyethylene groups with respect to oxyalkylene groups in the polymer compound constituting the adhesive in mass%.

Example 2 A laminated scourer was obtained by high-frequency heating in the same manner as in Example 1 except that the following adhesive was used instead of the adhesive A, and the curing time was evaluated in the same manner. The results were as shown in Table 1. The adhesive used here is adhesive A8
3 parts by mass, polyoxypropylene glycol (average molecular weight = 1500), and 4,4′-diphenylmethane diisocyanate are reacted with each other so that the content of terminal NCO groups becomes 5%. And 17 parts by mass of a moisture-curable polyurethane resin-based adhesive (hereinafter referred to as “adhesive B”).

Example 3 In place of adhesive A, 67 parts by weight of adhesive A and adhesive B33
Other than using an adhesive in which the parts by mass are uniformly mixed,
Laminated sashimi was obtained by high-frequency heating in the same manner as in Example 1, and the curing time was evaluated in the same manner. The results were as shown in Table 1.

Example 4 Instead of the adhesive A, 50 parts by mass of the adhesive A and the adhesive B50
Other than using an adhesive in which the parts by mass are uniformly mixed,
Laminated sashimi was obtained by high-frequency heating in the same manner as in Example 1, and the curing time was evaluated in the same manner. The results were as shown in Table 1.

Example 5 Instead of the adhesive A, 33 parts by weight of the adhesive A and the adhesive B67 were used.
Other than using an adhesive in which the parts by mass are uniformly mixed,
Laminated sashimi was obtained by high-frequency heating in the same manner as in Example 1, and the curing time was evaluated in the same manner. The results were as shown in Table 1.

Example 6 Instead of the adhesive A, 17 parts by mass of the adhesive A and the adhesive B83 were used.
Other than using an adhesive in which the parts by mass are uniformly mixed,
Laminated sashimi was obtained by high-frequency heating in the same manner as in Example 1, and the curing time was evaluated in the same manner. The results were as shown in Table 1.

Comparative Example 1 A laminated scourer was obtained by high-frequency heating in the same manner as in Example 1 except that the adhesive B was used instead of the adhesive A, and the curing time was evaluated in the same manner. The results were as shown in Table 1.

[0022]

[Table 1]

As is clear from the results in Table 1, Example 1
In the methods according to Nos. To 6, it can be seen that the adhesive hardens when the high frequency application time is 20 to 50 seconds. On the other hand, in the method according to Comparative Example 1, it can be seen that the adhesive is not sufficiently cured even if the high frequency time exceeds 50 seconds. Further, it can be seen that the higher the abundance of oxyethylene groups in the polymer compound constituting the adhesive, the more the adhesive cures even when the high frequency application time is short. Therefore, it is also understood that there is a causal relationship between the high frequency heating and the presence of the oxyethylene group.

Example 7 A laminated scourer was obtained by high-frequency heating in the same manner as in Example 1 except that the following adhesive was used instead of the adhesive A, and the curing time was evaluated in the same manner. . The adhesive used here was polyoxypropylene glycol (average molecular weight = 1).
400), polyoxypropylene polyoxyethylene glycol (average molecular weight = 1500, polyoxypropylene group: polyoxyethylene group = 93: 7) obtained by polycondensation of polyoxyethylene glycol, and 4,4 ′
-Diphenylmethane diisocyanate with terminal NCO
It is a moisture-curable polyurethane resin-based adhesive made of a polymer compound obtained by reacting so that the group content becomes 5%. As a result, in high-frequency heating for 10 to 40 seconds,
The nonwoven fabric or the urethane sponge was peeled off without breaking, but the high frequency heating for 50 seconds could not be peeled without breaking the nonwoven fabric or the urethane sponge.
Thus, the use of this adhesive allowed the curing time to be about 50 seconds.

Example 8 A laminated scourer was obtained by high frequency heating in the same manner as in Example 1 except that the following adhesive was used in place of the adhesive A, and the curing time was evaluated in the same manner. . The adhesive used here was polyoxypropylene glycol (average molecular weight = 1).
350), polyoxypropylene polyoxyethylene glycol (average molecular weight = 1500, polyoxypropylene group: polyoxyethylene group = 9: 1) obtained by polycondensation of polyoxyethylene glycol, and 4,4 ′ −
This is a moisture-curable polyurethane resin-based adhesive made of a polymer compound obtained by reacting diphenylmethane diisocyanate with a terminal NCO group content of 5%. As a result, with high-frequency heating for 10 to 40 seconds, the non-woven fabric or urethane sponge was peeled off without breaking the material,
By the high-frequency heating for 50 seconds, the nonwoven fabric or the urethane sponge could not be peeled without breaking. Thus, the use of this adhesive reduces its cure time by about 50
Seconds.

Example 9 A laminated scourer was obtained by high-frequency heating in the same manner as in Example 1 except that the following adhesive was used in place of the adhesive A, and the curing time was evaluated in the same manner. . The adhesive used here was Pluronic L34 (a polyether polyol manufactured by Asahi Denka Kogyo Co., Ltd., average molecular weight = 1600, number of functional groups = 2,
Polyoxypropylene group: polyoxyethylene group = 6:
This is a moisture-curable polyurethane resin-based adhesive comprising a polymer compound obtained by reacting 4) with 4,4′-diphenylmethane diisocyanate so that the content of terminal NCO groups becomes 5%. As a result, the high-frequency application time during which the nonwoven fabric or urethane sponge could not be peeled off without breaking the material was 15 seconds. 60% R at 23 ° C
When curing under the atmosphere of H, how long curing time,
As a result of evaluating whether or not the punching workability was good, the curing time was 60 hours. Here, whether or not the punching workability was good was evaluated by whether or not the adhesive adhered to the cutting blade. Table 2 shows these results.
It was shown to. In Table 2, the former high-frequency application time is shown as a curing time (second), and the latter is punching workability (hour).
As shown.

Example 10 A laminated scourer was obtained by high-frequency heating in the same manner as in Example 9 except that the spray amount of water was changed to 60 g / m ² , and evaluation of the curing time and punching workability were performed in the same manner. Was evaluated, and the results are shown in Table 2.

Example 11 Except that the spray amount of water was changed to 50 g / m ² , high-frequency heating was performed in the same manner as in Example 9 to obtain a laminated scourer, and evaluation of the curing time and punching workability were performed in the same manner. Was evaluated, and the results are shown in Table 2.

Example 12 Except that the spray amount of water was 30 g / m ² , high frequency heating was performed in the same manner as in Example 9 to obtain a laminated scourer, and evaluation of the curing time and punching workability were performed in the same manner. Was evaluated, and the results are shown in Table 2.

Example 13 Except that the spray amount of water was changed to 20 g / m ² , high frequency heating was performed in the same manner as in Example 9 to obtain a laminated scourer, evaluation of the curing time, and punching workability in the same manner. Was evaluated, and the results are shown in Table 2.

Example 14 A laminated scourer was obtained by high-frequency heating in the same manner as in Example 9 except that the spray amount of water was changed to 10 g / m ² , and evaluation of the curing time and punching workability were performed in the same manner. Was evaluated, and the results are shown in Table 2.

Comparative Example 2 Except that water was not sprayed, high frequency heating was performed in the same manner as in Example 9 to obtain a laminated scourer, and evaluation of the curing time was performed in the same manner.
Then, the punching workability was evaluated, and the results are shown in Table 2.

[0033]

[Table 2]

As is clear from Table 2, Examples 9 to 14
In the method according to (1), since the high-frequency heating is performed in the presence of water, the adhesive hardens in a relatively short time as compared with Comparative Example 2 in which the high-frequency heating is performed in the absence of water. Further, as is apparent from the results of the methods according to Examples 9 to 14, when the amount of water is 40 g / m ² or more, that is, 20% by mass or more based on the moisture-curable polyurethane resin-based adhesive, It can be seen that the effect is saturated when the curing time is shortest and longer.

[0035]

As described above, when producing a laminated scourer by laminating and bonding scrubbing pieces A and B, a moisture-curable polyurethane resin containing a polymer compound having a polyoxyethylene group in the molecular chain. When high-frequency heating is performed using a system adhesive in the presence of moisture, the adhesive is quickly cured. Accordingly, the scrubbing pieces A and B can be quickly laminated and bonded, and the scrubbing pieces A and B are laminated.
Need not be pressed for a long time. Therefore, it is possible to manufacture the laminated scourer in a short time, and it is possible to improve the production efficiency.

Claims (4)

[Claims] 1. A scouring piece different from the scrubbing piece A via at least one surface of the scrubbing piece A via a moisture-curable polyurethane resin-based adhesive containing a polymer compound having a polyoxyethylene group in a molecular chain. After laminating B, by applying high-frequency heating in the presence of moisture, the moisture-curable polyurethane resin-based adhesive is cured, and the scrubbing pieces A and the scrubbing pieces B are bonded to each other. How to make eagle. 2. The method for producing a laminated scourer according to claim 1, wherein the scrubber pieces A are made of non-woven fabric and the scrubber pieces B are made of sponge. 3. The laminated scourer according to claim 1, wherein a moisture-curable polyurethane resin-based adhesive containing a polymer compound having a polyoxyethylene group in a molecular chain and a polymer compound having a polyoxypropylene group in a molecular chain is used. Production method. 4. A polyoxyethylene group having a molecular chain,
The method for producing a laminated scourer according to any one of claims 1 to 3, wherein a polymer compound having a terminal NCO group is used.