JP3394659B2 - Waterproof seal material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fixed water-stop seal material using a foamed structure having closed cells or both closed and open cells.

[0002]

2. Description of the Related Art A rubber foam has excellent cushioning properties and is useful for applications such as cushioning materials and patch materials. Comparing closed cells and open cells in a foamed structure, the former has a structure in which the cells are partitioned by a partition in a three-dimensional lattice shape, while the latter has a partition between a series of partitioned cells removed. The latter structure is easier to mechanically deform. However, while open cells cannot be expected to have a water blocking effect at all, closed cells can be expected to have a water blocking effect due to partition walls between the bubbles.

A foamed structure having both closed cells and open cells (hereinafter, also referred to as "half-semi-semi-opened foamed structure") is a work for filling a complicated gap due to easy deformation based on the open cells. It is suitable as a standard water-stop seal material that can be used by filling in complex gaps, because both ease of use and water-stoppage due to closed cells can be expected.

[0004]

However, according to the test results conducted by the present inventors, in the case of using a closed-cell foam structure or a semi-reinforced foam structure as a waterproof seal material. , With the passage of time, the repulsive stress as the foam structure is relieved, the contact surface pressure between the foam structure and the adherend interface is reduced accordingly, and water leakage occurs along this interface,
It was found that it cannot be effectively used as a water-stop seal material.

In order to solve this problem, it is conceivable to provide a pressure-sensitive adhesive layer on both surfaces of the foamed structure to bond the adherend interface. However, if a general acrylic or rubber adhesive is used as the adhesive layer, these adhesives exhibit adhesive strength at the same time as they are assembled, and therefore it is difficult to reposition them and the sealing work is likely to be hindered.

In view of such circumstances, the present invention provides a fixed water-stop seal material by providing a specific pressure-sensitive adhesive layer in a foam structure having closed cells or both closed cells and open cells. The purpose is to enable effective use as.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made earnest studies on the above-mentioned object, and as a result, have found that a polycarbonate structure is formed on the surface of a closed cell foam structure or a semi-reinforced foam structure. When a pressure-sensitive adhesive layer containing a specific polymer having the above is provided, the above-mentioned pressure-sensitive adhesive layer does not have tack when assembled on the part where water is stopped, so that it does not adhere immediately, and therefore It can be easily repositioned so that assembly work can be done without problems, and after assembly, it gradually adheres due to the repulsive force of the foamed structure, and the sealability between the surface of the foamed structure and the interface of the water stop part is remarkable. Knowing that it will increase, the present invention has been completed.

That is, the present invention provides the following formula on at least one surface of a foam structure having closed cells or both closed and open cells. A polymer having a repeating unit represented by (R is a linear or branched hydrocarbon group having 2 to 20 carbon atoms).
The present invention relates to a waterproof seal material, which has a layer composed of an adhesive composition containing polyester as a polymer having a bone structure. Further, the present invention provides a layer comprising a pressure-sensitive adhesive composition containing polyester as a polymer having a polycarbonate structure on one surface of the foamed structure, and an acrylic pressure-sensitive adhesive on the opposite surface. It is possible to provide a water-stop seal material having the above-mentioned structure, which is formed by providing a layer or a rubber-based pressure-sensitive adhesive layer and laminating a release liner thereon.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The pressure-sensitive adhesive composition used in the present invention has the following formula: A polymer having a repeating unit represented by (R is a linear or branched hydrocarbon group having 2 to 20 carbon atoms).
It comprises a polymer having a bone structure, and the polymer has a weight average molecular weight of 10,000 or more, preferably 30,000 or more, more preferably 50,000 or more (usually up to 300,000).
It should be

The above-mentioned polymers include polyesters synthesized from polycarbonate (or its derivative) and dicarboxylic acid, polyesters synthesized from polycarbonate dicarboxylic acid and diol, and the like. Polyester synthesized from polycarbonate and dicarboxylic acid is particularly preferable.

This polyester essentially comprises a diol component essentially including polycarbonate diol and a dicarboxylic acid having a molecular skeleton of an aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms. According to a conventional method, the above dicarboxylic acid component is subjected to an esterification reaction with no catalyst or an appropriate catalyst to obtain the compound. In this reaction, the diol component and the dicarboxylic acid component are preferably equimolar reaction so that the molecular weight of the obtained polyester is in the above range, but in order to accelerate the esterification reaction, some May be used in excess for the reaction.

Polycarbonate used here
Le is the following formula; (R is a linear or branched hydrocarbon group having 2 to 20 carbon atoms) having a repeating unit represented by a number average molecular weight of 400 or more, preferably 900 or more (usually 1 or more). Up to ten thousand). Specifically, polyhexamethylene carbonate, diol, poly (3-methylpentene carbonate) diol, polypropylene carbonate diol, and mixtures and copolymers of these can be used. is there. As commercially available products, there are "PLACCEL CD205PL" and "CD208 CD" manufactured by Daicel Chemical Industries, Ltd.
PL ”,“ CD210PL ”,“ CD220P ”
L ”,“ CD205HL ”,“ CD208HL ”,
Examples thereof include "CD 210HL" and "CD220HL".

As a diol component, if necessary, ethylene glycol, propylene glycol, butanediol
A straight-chain diol such as diol, hexanediol, octanediol, decanediol and octadecanediol or a branched diol may be used in combination. These diols are used in an amount of 50% by weight or less, preferably 30% by weight or less based on the total amount of the diol components. Further, in order to make the polymer have a high molecular weight, a small amount of a trifunctional or higher functional polyol component may be added.

The dicarboxylic acid component has 2 to 2 carbon atoms.
20 aliphatic or alicyclic hydrocarbon groups are used as a molecular skeleton, and the above hydrocarbon groups may be linear or branched. Specifically, succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid,
Examples thereof include sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, their acid anhydrides and lower alkyl esters.

In the present invention, a polymer having a polycarbonate structure such as polyester is usually used.
Can be crosslinked by an appropriate means to obtain a tack-free pressure-sensitive adhesive composition having excellent durability such as heat resistance.
The crosslinking method may be arbitrary, but in general, a method using a so-called crosslinking agent in which a compound having a functional group capable of reacting with a hydroxyl group and / or a carboxyl group contained in a polymer such as polyester is added and reacted is preferable. Examples of the cross-linking agent include polyisocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds, metal alkoxide compounds and the like, and polyisocyanate compounds are particularly preferably used.

As the polyisocyanate compound, lower aliphatic polyisocyanates such as ethylene diisocyanate, butylene diisocyanate and hexamethylene diisocyanate, cyclopentylene diisocyanate,
Alicyclic polyisocyanates such as cyclohexylene diisocyanate and isophorone diisocyanate, 2,4
-Aromatic polyisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate are available, and tolylene diisocyanate of trimethylol propane is also available. Ne-
The adduct, hexamethylene diisocyanate adduct and the like are also used.

These cross-linking agents can be used alone or in a mixture of two or more kinds. The amount used depends on the balance with the polymer such as polyester to be crosslinked.
Further, it is appropriately selected depending on the purpose of use of the pressure-sensitive adhesive composition.
Generally, the ratio of 0.5 to 5 parts by weight with respect to 100 parts by weight of a polymer such as polyester is preferable, which facilitates the adhesiveness and the mounting work for exhibiting the sealing property. A good result is obtained in the balance characteristic with the tack free.

The pressure-sensitive adhesive composition used in the present invention may contain various conventionally known tackifiers. Blending of a tackifier may facilitate balance between adhesive strength and durability. In addition, various conventionally known additives such as inorganic or organic fillers, powders of metal powders and pigments, particles, foils and the like can be arbitrarily blended. further,
You may make it improve durability by adding an antioxidant.

As the foamed structure used in the present invention, various known ones can be used as long as they have closed cells or both open cells and closed cells. To manufacture this foamed structure, natural rubber or synthetic rubber (chloroprene rubber, ethylene-propylene-terpolymer, etc.), vulcanizing agent, foaming agent, filler, etc. are used in a Banbury mixer or a pressure kneader.
After kneading with a kneader such as a dough, it is continuously kneaded with a calendar, an extruder, a conveyor belt casting, etc. while being molded into a sheet shape, a rod shape, which is heated to be vulcanized and foamed, If necessary, the vulcanized foam may be cut into a predetermined shape, or natural rubber or synthetic rubber, a vulcanizing agent, a foaming agent, a filler, and the like may be kneaded with a mixing ball or the like, and the kneaded composition may be batched. Depending on the formula, methods such as vulcanization, foaming and molding in a mold can be used.

The waterproof sealing material of the present invention is obtained by applying the above-mentioned pressure-sensitive adhesive composition onto such a foamed structure so that the thickness after drying is usually about 2 to 100 μm. A layer comprising the above-mentioned pressure-sensitive adhesive composition is supported on a foam structure. The layer composed of the pressure-sensitive adhesive composition may be provided not only on one surface of the foamed structure but also on both surfaces of the foamed structure if necessary. The layer composed of the pressure-sensitive adhesive composition thus provided,
Since it does not have tack by itself, it is not necessary to attach a release liner on top of this, there is no need to peel off the liner when using it, and it is easy to reposition during installation, so installation work It is extremely superior in sex.

When a layer comprising the above-mentioned pressure-sensitive adhesive composition is provided on only one side of the foamed structure, an acrylic pressure-sensitive adhesive layer or a rubber-based pressure-sensitive adhesive layer is used as a general-purpose pressure-sensitive adhesive on the opposite side of the foamed structure. You may make it provide an agent layer. In this case, since these pressure-sensitive adhesive layers have tack, a release liner is usually attached thereon. At the time of attaching to the part to be stopped water, first, positioning is performed by using the layer made of the above-mentioned adhesive composition having no tack provided on one side, and then peeling off the release liner on the opposite side and adhering. You can use a method such as sealing.

[0022]

EXAMPLES Next, examples of the present invention will be described to more specifically describe. In the following, "parts" means "parts by weight".

Example 1 The following compounding composition was kneaded with a mixing ball, and the kneaded material was heated in an oven at 160 ° C. for 30 minutes for vulcanization and foaming, and taken out from the oven. After cooling, a part of the bubbles was broken by a pressure method to obtain a semi-german semi-continuous foamed structure. The specific gravity of this foamed structure was 0.11 g / ml. <Composition of foamed structure> Ethylene / propylene / terpolymer 100 parts Zinc white 5 parts Stearic acid 1 part Carbon 40 parts Polyethylene 20 parts Heavy calcium carbonate 180 parts Polybutene 40 parts Sulfur 2 parts Mercaptobenzothiazo -Rule 1 part Diethyldithiocarbamate zinc 2 parts Azodicarboxylic acid amide 13 parts

On the other hand, a four-necked separable flask was equipped with a stirrer, a thermometer and a water separation tube, to which polycarbonate carbonate [PLA manufactured by Daicel Chemical Industries, Ltd.
CCEL CD220PL ", hydroxyl value: 55.4KO
Hmg / g] 500 g, sebacic acid 50 g, and dibutyltin oxide 123 mg as a catalyst were charged, and in the presence of a small amount of toluene as a reaction water discharge solvent, the temperature was raised to 180 ° C. with stirring and maintained at this temperature. . After a while, outflow separation of water was observed and the reaction started to proceed. The reaction was continued for about 50 hours, and the weight average molecular weight was 4
A polyester of 7,000 was obtained.

After diluting this polyester with toluene to a solid content concentration of 25% by weight, a hexamethylene diisocyanate adduct of trimethylolpropane as a cross-linking agent is added to 100 parts (solid content) of the polyester [Nippon Polyurethane Co., Ltd. 2) (solid content)
It was added to give an adhesive composition. Next, this pressure-sensitive adhesive composition was applied to one surface of the semi-lubricated semi-continuous foamed structure by an applicator and dried at 130 ° C. for 5 minutes to give a pressure-sensitive adhesive composition having a thickness of 30 μm. Was formed. Further, an acrylic pressure-sensitive adhesive layer having a thickness of 150 μm was provided on the opposite surface side of this layer, and a release liner was provided on the acrylic pressure-sensitive adhesive layer to obtain a waterproof seal material.

Example 2 The thickness of a layer made of a pressure-sensitive adhesive composition containing polyester was 5
A waterproof seal material was produced in the same manner as in Example 1 except that the thickness was changed to μm.

Example 3 The following compounding composition was kneaded with mixin-gall, and the kneaded material was heated in an oven at 160 ° C. for 30 minutes to be vulcanized and foamed to obtain a foam structure having closed cells. Obtained. The specific gravity of this foam structure was 0.10 g / ml. <Composition composition of foamed structure> Ethylene / propylene / terpolymer 40 parts Butyl rubber 60 parts Zinc white 5 parts Stearic acid 3 parts Carbon 50 parts Heavy calcium carbonate 50 parts Process oil 20 parts Sulfur 0.5 parts Mercapto Benzothiazole 1 part Zinc diethyldithiocarbamate 1 part Quinonedioxime 0.5 part Quinonemonooxime 0.5 part Azodicarboxylic acid amide 20 parts

The pressure-sensitive adhesive composition obtained in Example 1 was applied to one surface of the closed-cell foam structure by an applicator and dried at 130 ° C. for 5 minutes to give a pressure-sensitive adhesive having a thickness of 30 μm. A layer of the composition was formed. Further, an acrylic pressure-sensitive adhesive layer having a thickness of 150 μm was provided on the opposite surface of this layer, and a release liner was provided thereon to obtain a water-stop seal material.

Comparative Example 1 An acrylic pressure-sensitive adhesive layer having a thickness of 150 μm was provided on one surface of the semi-lubricated semi-continuous foamed structure obtained in Example 1, and a release liner was provided thereon to provide a water-proof sheet. It was made of wood.

Comparative Example 2 A 150 μm thick acrylic pressure-sensitive adhesive layer was provided on one side of the closed cell foam structure obtained in Example 3, and a release liner was provided thereon to provide a water-stop sealant. And

For each of the water-stop seal materials of Examples 1 to 3 and Comparative Examples 1 and 2, as a water stop test, a U-shaped water stop test and a high-pressure running water stop test were conducted by the following method. Ivy. The results are as shown in Table 1 below.

<U-shaped water stop test> Water-stop seal material, thickness 1
Sample A was processed into a string having a square cross section with a width of 0 mm and a width of 10 mm. As shown in FIGS. 1 and 2, this sample A is U-shaped and sandwiched between two acrylic plates 1 and 1, and the space between the acrylic plates 1 and 1 is maintained with a space maintained by a spacer 2. Fastened with bolts and nuts 3. The compressibility of the sample A in the thickness direction was adjusted according to the thickness of the spacer 2.

After the bolts and nuts 3 were fastened in this way, as shown in FIG. 3, the head h = 1 in the U-shape of the sample A.
Water 4 was added at 00 mm. After fastening the bolts and nuts 3 and leaving them in an atmosphere of 80 ° C. for 168 hours, the temperature was returned to room temperature, and in the same manner as described above, the water head h = 10 in the U-shape of the sample A.
Water 4 was added at 0 mm. Immediately after assembling the former, the latter 80
As a U-shaped water stopping test after 168 ° C. for 168 hours, it was examined whether or not water can be stopped when the compressibility in the thickness direction of Sample A was set to%.

<High-pressure running water stop test> A water-stop seal material was processed into a donut shape having a thickness of 10 mm, an outer diameter of 100 mm, and an inner diameter of 80 mm to obtain a sample B. This sample B is shown in FIGS.
As shown in Fig. 4, the acrylic plate 1 and the acrylic molded body 5 were sandwiched, and the space between the acrylic plate 1 and the acrylic molded body 5 was fastened with the bolts and nuts 3 while the space was maintained by the spacer 2 which passed through the bolt portion. . The compressibility of the sample B in the thickness direction was adjusted by the thickness of the spacer 2. After tightening with bolts and nuts 3 in this way, 80 kgf / c from a distance of 300 mm
Water was applied for 3 minutes with the pressure of m ² aimed at the portion of the waterproof sealant. It was investigated whether the compressibility of the sample B in the thickness direction was set to what percentage and whether the water could be stopped.

[0035]

As is clear from the results shown in Table 1 above, each of the water-stop sealing materials of Examples 1 to 3 of the present invention has a very good water-stop property with a low compressibility of the foam structure. Is obtained,
Even if the repulsive stress relaxes with the passage of time, the waterproofness does not decrease,
Further, it can be seen that it shows high water stopping performance against high-pressure running water.

[0037]

As described above, the present invention provides a pressure-sensitive adhesive composition containing a specific polymer having a polycarbonate structure on the surface of a foam structure having closed cells or both open cells and closed cells. Since there is no tack, it does not adhere immediately because of the provision of the layer made of material, and therefore the installation work can be done easily, and after the installation, it gradually adheres due to the repulsive force of the foam structure. However, it is possible to provide an excellent water-sealing seal material in which the sealing property between the surface of the foam structure and the interface of the adherend is enhanced.

Further, since the layer comprising the above-mentioned pressure-sensitive adhesive composition has no tack, it is not necessary to attach a release liner on this layer, and there is no trouble of peeling off the release liner at the time of use. Installation work of water seal material becomes easier. Further, a layer provided with the above-mentioned pressure-sensitive adhesive composition on one side, and a general-purpose acrylic pressure-sensitive adhesive layer or rubber-based pressure-sensitive adhesive layer provided on the opposite side, without losing the above advantages, the general-purpose pressure-sensitive adhesive It is also possible to take advantage of the characteristics of the agent layer.

[Brief description of drawings]

FIG. 1 is a side view showing an apparatus configuration of a U-shaped water stop test of a water stop seal material.

FIG. 2 is a sectional view taken along line II-II in FIG.

FIG. 3 is a cross-sectional view showing a state in which water is put into a U-shaped sample (water blocking seal material) in the apparatus configuration of FIGS. 1 and 2.

FIG. 4 is a side view showing a device for a high-pressure running water stop test of a water-stop seal material.

5 is a sectional view taken along line VV in FIG.

[Explanation of symbols]

A, B sample (water-stop seal material) 1 acrylic board 2 Spacers 3 bolt nuts 4 water 5 Acrylic molding

Front page continuation (72) Inventor Masahiko Ando, 1-2, Shimohozumi, Ibaraki, Osaka Prefecture Nitto Denko Corporation (56) Reference JP-A-51-122170 (JP, A) JP-A-8- 170065 (JP, A) JP-A-7-324183 (JP, A) JP-A-5-239202 (JP, A) Actual Kaihei 6-49071 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09K 3/10 C09J 169/00 C09J 167/00-167/08 C09J 175/00-175/16

Claims (2)

(57) [Claims] 1. The following formula on at least one surface of a foam structure having closed cells or both closed and open cells: (R is a straight-chain or branched hydrocarbon group having 2 to 20 carbon atoms) and a pressure-sensitive adhesive composition containing polyester as a polymer having a polycarbonate structure having a repeating unit represented by A waterproof sealing material having a layer. 2. A polycarbonate panel on one surface of the foam structure.
A layer composed of a pressure-sensitive adhesive composition containing polyester as a polymer having a structure with a transparent structure is provided, and an acrylic pressure-sensitive adhesive layer or a rubber pressure-sensitive adhesive layer is provided on the opposite surface, and a release liner is bonded onto it. The waterproof sealing material according to claim 1, wherein