JP4943992B2 - Laminated sponge and method for producing the same - Google Patents

Description

  The present invention relates to a laminated sponge used together with a cleaning agent containing an organic solvent and a method for producing the same.

Among dirt adhering to the body of a vehicle such as an automobile, it is known that particularly dirt due to tar pitch is difficult to clean. This tar pitch is a constituent of asphalt, and it adheres to the body of the car by the tire jumping up when the car runs on the asphalt road surface that is not dry after paving, for example. , Become dirty. Dirt caused by tar pitch cannot be easily washed off by normal car washing operations, so it contains a special washing that contains organic solvents such as alcohol, toluene, hydrocarbon solvents, petroleum solvents, etc. to the extent that it does not damage the car body. The agent is used. Such a cleaning agent is usually adjusted to a low viscosity, and as a cleaning method, the cleaning agent is impregnated into a sponge scrubbing or the like to scrape off dirt.
Since the cleaning agent contains an organic solvent, in consideration of safety, the sponge scrubbing has a structure that makes it difficult for the organic solvent to adhere to the hand, for example, the gripping part and the cleaning agent are easily impregnated and have dirt. Laminated sponge scrubbers having a foamed portion that easily spreads the cleaning agent on the surface are widely used.

Patent Document 1 discloses a laminate formed by adhering polyethylene foam and urethane foam. After applying an emulsion primer in advance to polyethylene foam, a reactive hot melt adhesive is applied to join the urethane foam. This is manufactured.
Patent Document 2 discloses a laminate comprising a polyurethane foam and a polyethylene resin molded product having a specific number of cells, and the joint surface between the two is melted in advance and pressed as it is. ing.

JP-A-8-336268 JP-A-10-305514

According to the laminates disclosed in Patent Documents 1 and 2, delamination may occur when a cleaning agent containing an organic solvent is used.
An object of the present invention is to provide a laminated sponge containing an organic solvent and having excellent resistance to a cleaning agent, a polishing agent (wax, etc.), a coating agent, and the like, and a method for producing the same.

The present invention is shown below.
1. Heat-treated polyolefin foam layer, adhesive layer formed on the heat-treated surface of the polyolefin foam layer and cured using a reactive adhesive, and bonded to the surface of the adhesive layer A laminated sponge comprising a polyurethane foam layer sequentially.
2. 2. The laminated sponge according to 1 above, wherein the surface of the polyurethane foam layer is subjected to film removal treatment.
3. 3. The laminated sponge according to 1 or 2 above, wherein the reactive adhesive is a urethane adhesive.
4). 4. The laminated sponge according to any one of 1 to ³ above, wherein the polyolefin foam layer has a density of 0.020 to 0.070 g / cm ³ .
5. A heating step of heating the surface of the polyolefin foam to melt the surface layer portion; a coating step of applying a reactive adhesive to the heat-treated surface of the polyolefin foam to form an adhesive layer; and polyurethane foam A pressure bonding step of pressing the polyolefin foam and the polyurethane foam, and the reactive adhesive is reaction-cured to form the polyolefin foam and the polyurethane foam. A method for producing a laminated sponge, characterized by bonding.
6). 6. The method for producing a laminated sponge according to 5 above, wherein the surface of the polyurethane foam is subjected to film removal treatment.
7). 7. The method for producing a laminated sponge according to 5 or 6 above, wherein the reactive adhesive is a urethane adhesive.
8). 8. The method for producing a laminated sponge according to any one of 5 to 7, wherein the polyolefin foam has a density of 0.020 to 0.070 g / cm ³ .

According to the laminated sponge of the present invention, since it has excellent solvent resistance and excellent adhesion between the polyolefin foam layer and the polyurethane foam layer, it can be used as a kind of cleaning agent, polishing agent (wax etc.), coating agent, etc. Regardless, it has excellent shape retention and can be used for a long time. Further, even when used for oil stains that are difficult to wash, the polyolefin foam layer and the polyurethane foam layer can be stably washed without peeling off.
When the reactive adhesive is a urethane-based adhesive, the adhesion between the polyolefin foam layer and the polyurethane foam layer is particularly excellent. When the reactive adhesive is impregnated with a cleaning agent containing an organic solvent, the two peel off. Without solvent, it has excellent solvent resistance.
When the density of the polyolefin foam is 0.020 to 0.070 g / cm ³ (about 50 to 14 times as the expansion ratio), the strength of the laminated sponge is excellent.
Moreover, according to the method for producing a laminated sponge of the present invention, a laminated sponge having excellent solvent resistance and excellent durability can be produced efficiently.
When the reactive adhesive is a urethane adhesive, the adhesion between the polyolefin foam layer and the polyurethane foam layer is particularly excellent.
In addition, when the density of the polyolefin foam is 0.020 to 0.070 g / cm ³ (about 50 to 14 times as the expansion ratio), it is possible to design a lightweight and obtain flexibility of the material. Become.

  The present invention will be described in detail below. In the present invention, “(co) polymerization” means homopolymerization and copolymerization.

1. Laminated sponge The laminated sponge of the present invention is a polyolefin foam layer whose surface is heat-treated, an adhesive layer formed on the heat-treated surface of the polyolefin foam layer, and cured using a reactive adhesive And a polyurethane foam layer bonded to the surface of the adhesive layer in order. That is, in the laminated sponge of the present invention, the polyolefin foam layer and the polyurethane foam layer are bonded via the adhesive layer.
The laminated sponge of the present invention is preferably used as a cleaning tool that is impregnated with a vehicle cleaning agent, a polishing agent or the like containing 20% by mass or more of an organic solvent such as alcohol or petroleum-based solvent.

The polyolefin foam layer can be formed of an olefin resin composition containing an olefin polymer.
Examples of the olefin polymer include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / octene-1 copolymer, ethylene / propylene / non-conjugated diene terpolymer (EPDM) and the like. Α-olefin copolymer rubber; isotactic copolymer resin of polyethylene, polypropylene, propylene and other α-olefins such as ethylene, butene-1, pentene-1, hexene-1 (block, random) (Co) polymer resin containing one or more units composed of ethylene and α-olefin having 2 to 20 carbon atoms, such as ethylene, and a copolymer of an unsaturated compound having a functional group An ethylene copolymer; a graft-modified olefin system obtained by graft-copolymerizing an unsaturated compound having a functional group to the (co) polymer resin. Butter, and the like can be mentioned.
Examples of unsaturated compounds having functional groups include unsaturated carboxylic acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, amino group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, and isocyanate group-containing unsaturated compounds. Examples include compounds, unsaturated carboxylic acid alkyl esters, vinyl esters, ethylenically unsaturated ether compounds, aromatic vinyl compounds, and diene compounds.
The glass transition temperature of the olefin polymer is not particularly limited.

The olefin-based resin composition may contain additives such as a plasticizer, an antioxidant, and a colorant.
The melt index etc. of the said olefin resin composition are not specifically limited.

The polyolefin foam layer may have either a closed cell structure or an open cell structure. However, the cleaning agent, the polishing agent or the like does not ooze out from the portion to be the gripping part (the hand is difficult to get dirty), the excess cleaning agent, the glossy It is preferable to have a closed cell structure because it is not necessary to use an extractant or the like and the mechanical strength is excellent.
The density of the polyolefin foamed layer is not particularly limited, usually, (approximately 50 to 14 times expansion ratio) 0.020~0.070g / cm ^3, preferably 0.025~0.050g / cm ³ (Expansion ratio is about 40 to 20 times). When the density is in the above range, the material can be designed to be lightweight and the flexibility of the material can be obtained.

  The surface of the polyolefin foam layer, that is, the surface facing the adhesive layer is heat-treated, and may be either a flat surface or a curved surface, and may have a concave portion, a convex portion, a groove portion, and the like. Moreover, since it is heat-treated, an aspect in which surface modification by oxidation or the like is performed on only the outermost surface while maintaining the surface shape, or an arbitrary thickness from the surface to a depth of about 3 mm The surface layer can be melted to be a flat surface (the porosity is decreased and the density is increased) and the outermost surface is oxidized or the like. In addition, about heat processing conditions, it explains in full detail in description of a manufacturing method.

  Although the thickness of the said polyolefin foamed layer is not specifically limited, Usually, 10-50 mm, Preferably it is 15-40 mm.

The adhesive layer is a layer formed on the heat-treated surface of the polyolefin foam layer and cured by using a reactive adhesive.
As reactive adhesives, urethane-based, polyester-based, acrylic-based, cyanoacrylate-based, phenol-based, urea resin-based, melamine-resin-based, epoxy-based, silicone rubber-based, modified silicone-based compositions, and the like are used. A layer is comprised by the reaction hardened | cured material of the component contained in this composition. A preferred reactive adhesive is a urethane-based adhesive because the resulting laminated sponge is excellent in solvent resistance.
The reactive adhesive will be described in detail in the description of the method for producing a laminated sponge.

Although the thickness of the said adhesive layer is not specifically limited, The absolute dry mass of an adhesive layer is 10-120 g / m < ² > normally, Preferably it is 30-70 g / m < ² >.

  The polyurethane foam layer may be formed based on a polyaddition reaction or a polymerization reaction of isocyanate, and in particular, may be formed of a foam raw material including a polyol, an isocyanate, a catalyst, and a foaming agent. it can. This foaming material further includes foam stabilizers, chain extenders, crosslinking agents, foam breakers, antifoaming agents, plasticizers, antioxidants, UV absorbers, anti-aging agents, flame retardants, stabilizers, colorants, etc. It may contain.

Examples of the polyol include polyether polyol, polyester polyol, epoxy resin-modified polyol, acrylic polyol, polybutadiene polyol, and silicone polyol. Among these, polyether polyol and polyester polyol are preferable, and polyester polyol is particularly preferable because of excellent solvent resistance.
Polyether polyols include polypropylene glycol; polytetramethylene glycol; polyether polyols obtained by addition polymerization of propylene oxide and ethylene oxide to polyhydric alcohols such as glycerin, dipropylene glycol, and trimethylolpropane; Examples include the body.
The polyether polyol may be a polyether ester polyol. In that case, as the polyether ester polyol, polyalkylene polyols such as polyethylene glycol, polypropylene glycol, and propylene oxide adducts of glycerin, polycarboxylic acid anhydrides such as succinic anhydride, adipic anhydride, and phthalic anhydride, and ethylene oxide And compounds obtained by reacting with a compound having a cyclic ether group such as propylene oxide.
Polyester polyols include condensation polyester polyols obtained by reacting polycarboxylic acids such as adipic acid and phthalic acid with polyols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin; lactone polyester polyols; polycarbonates A polyol etc. are mentioned.

  As the isocyanate, tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI) , Dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), and modified products thereof.

Catalysts include amine-based catalysts such as monoamines, diamines, triamines, polyamines, cyclic amines, alcohol amines, ether amines; organometallic compounds such as organotin compounds, organomercury compounds, organolead compounds A catalyst is mentioned.
As an amine catalyst, triethylamine, N, N-dimethylcyclohexylamine, triethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane-1,3 -Diamine, N, N, N ', N'-tetramethylhexane-1,6-diamine, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N ', N ", N "-pentamethyldipropylenetriamine, tetramethylguanidine, N, N-dipolyoxyethylene stearylamine, N, N-dipolyoxyethylene tallow alkylamine, triethylenediamine, N, N'-dimethylpiperazine, N-methyl -N '-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N-ethylmorpholine, N- (N', N'-dimethyl) Tilaminoethyl) -morpholine, 1,2-dimethylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl)- Examples include piperazine, N- (2-hydroxyethyl) -morpholine, bis- (2-dimethylaminoethyl) ether, and ethylene glycol bis- (3-dimethyl) -aminopropyl ether.
Also, organometallic compound-based catalysts include tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin mercaptide, dioctyltin thiocarboxylate, lead octenoate , Lead naphthenate, potassium octylate, zinc neodecanoate and the like.
As the foaming agent, water is usually used. If necessary, a halogenated hydrocarbon, a low boiling point hydrocarbon, a liquefied carbon dioxide gas or the like may be used.

  The polyurethane foam layer is preferably a polyester polyurethane foam layer because of its excellent solvent resistance. In particular, excellent adhesion between the polyolefin foam layer and the polyurethane foam layer can be maintained over a long period of time even when a cleaning agent containing an organic solvent is used against dirt that adheres to the body of a vehicle and is difficult to remove. Can be maintained across.

The polyurethane foam layer preferably has an open-cell structure because it has excellent detergent permeability.
Further, the surface of the polyurethane foam layer may be subjected to film removal treatment or may not be subjected to film removal treatment. This film removal treatment refers to a treatment in which most of the cell film is removed and only the skeleton is formed. When the film removal treatment is performed, the permeability and retention of the cleaning agent are higher and the workability tends to be higher than when the film removal treatment is not performed. In addition, as a film removal treatment method, a blast treatment, a combustion treatment, a dissolution treatment and the like are known methods.

The density of the polyurethane foam layer, the number of cells, etc. are not particularly limited. The density is usually 0.020 to 0.100 g / cm ³ , preferably 0.030 to 0.080 g / cm ³ . The number of cells is usually designed to be 10 to 90/25 mm, preferably 40 to 80/25 mm. When the number of cells is small (when the cells are rough), liquid detergents, polishes, etc. cannot be retained by the polyurethane foam layer, and the effects of detergents, polishes, etc. may be difficult to express. On the other hand, when the number of cells is large (when the cells are fine), cleaning agents, polishes, etc. may not easily penetrate into the polyurethane foam layer and may be difficult to hold. It becomes difficult. In addition, as use continues, clogging is likely to occur, and the cleaning effect may be reduced.

  Although the thickness of the said polyurethane foam layer is not specifically limited, Usually, 5-30 mm, Preferably it is 10-20 mm.

  The laminated sponge of the present invention will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view showing an example of a laminated sponge 1, a polyolefin foam layer 11 whose surface is heat-treated, and a heat-treated surface of the polyolefin foam layer 11 which is formed by reactive adhesion. An adhesive layer 12 formed by curing using an agent and a polyurethane foam layer 13 bonded to the surface of the adhesive layer 12 are sequentially provided.

2. Manufacturing method of laminated sponge The manufacturing method of the laminated sponge according to the present invention includes a heating step of heating a surface of a polyolefin foam to melt a surface layer portion, and a reactive adhesion to the heat-treated surface of the polyolefin foam. An application step of applying an agent to form an adhesive layer, and a pressure-bonding step of bringing the polyurethane foam into contact with the adhesive layer and crimping the polyolefin foam and the polyurethane foam, the reactive type An adhesive is reactively cured to bond the polyolefin foam and the polyurethane foam.

  As the polyolefin foam and the polyurethane foam, foams obtained by using the respective forming materials for the polyolefin foam layer and the polyurethane foam layer in the description of the structure of the laminated sponge of the present invention can be used. In addition, it is preferable that the to-be-adhered surface of each foam has a surface shape which mutually contacts each other.

In the method for producing a laminated sponge of the present invention, first, the surface of the polyolefin foam is heated and the surface layer portion is melted by a heating step. The method of heating the polyolefin foam is not particularly limited, but a method of bringing a heating medium (heater) such as a heated metal plate or ceramic plate into contact with or approaching the surface of the foam is usually applied. Although the heating temperature and the heating time are not particularly limited, the heating temperature is usually higher than the softening temperature of the polyolefin resin composition constituting the polyolefin foam, and is preferably (softening temperature + 50) ° C. or higher (softening temperature + 200). ) C or less. For example, when the olefin polymer contained in the polyolefin resin composition is polyethylene (softening temperature 70 ° C.), the heating temperature is usually 200 to 400 ° C.
In addition, the thickness of the surface layer portion melted by heating (the length of the molten layer when viewed in the cross-sectional direction) is preferably 0.1 to 3 mm, more preferably from the viewpoint of the durability of the obtained laminated sponge. 0.5 to 1.0 mm. If the thickness is too short, the polyolefin foam layer and the polyurethane foam layer are easily peeled off when a cleaning agent containing an organic solvent is used.

  Next, in the application step, a reactive adhesive is applied to the heat-treated surface of the polyolefin foam to form an adhesive layer. The reactive adhesive is usually applied after the polyolefin foam reaches room temperature.

The coating amount of the reactive adhesive in the coating step is wet, preferably 20 to 120 g / m ² , more preferably 40 to 70 g / m ² . When the coating amount is in the above range, the adhesion between the polyolefin foam and the polyurethane foam is excellent.

As the reactive adhesive, as described above, urethane, polyester, acrylic, cyanoacrylate, phenol, urea resin, melamine resin, epoxy, silicone rubber, modified silicone, etc. Can be used. The composition may be one-pack type, two-pack type or more. Preferably, it is a urethane type adhesive.
The reactive adhesive may be either a moisture curable type or a thermosetting type, but is preferably a moisture curable type. The moisture curable adhesive may be either a room temperature curing adhesive or a hot melt adhesive, but is preferably a hot melt adhesive that is cured by moisture in the air.

The moisture curable hot melt adhesive is usually an adhesive in which a coating film formed at 80 to 140 ° C. is cured by moisture in the air.
A urethane-based adhesive preferable as the moisture-curable hot-melt adhesive is a composition mainly containing a prepolymer having an isocyanate group obtained by adding or copolymerizing an isocyanate or an alkoxy compound to a polyol.
Examples of the polyol include polyester polyol, polyether polyol, acrylic polyol, polybutadiene polyol, and hydrogenated polybutadiene all. These may be used alone or in combination of two or more.
Examples of the isocyanate include aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. These may be used alone or in combination of two or more.
In addition to the prepolymer having an isocyanate group, the urethane-based adhesive may contain a catalyst, a tackifying resin, and the like as necessary. In addition, it is preferable that this urethane type adhesive agent is a solventless type composition which does not contain an organic solvent.
Examples of the catalyst include tertiary amines such as triethylamine; tin-based catalysts such as stannic chloride; ammonium salts such as ammonium chloride. Examples of tackifying resins include styrene resins, terpene resins, and rosin esters.

  In the coating step, the reactive adhesive coating method includes brush coating, roller coating, spray coating, dipping (dipping), etc., but is not particularly limited, and is usually selected depending on the type, physical properties, and the like. .

Thereafter, in the pressure bonding step, the polyurethane foam is brought into contact with the adhesive layer before curing on the polyolefin foam, and the polyolefin foam and the polyurethane foam are pressure bonded. In addition, you may apply | coat the reactive adhesive to the to-be-adhered surface of a polyurethane foam before this crimping | compression-bonding process.
The pressing conditions in the said crimping | compression-bonding process are not specifically limited.
The reactive adhesive comes into contact with and presses the polyurethane foam and is cured by reaction to bond the polyolefin foam and the polyurethane foam. A laminated sponge having excellent adhesion can be obtained both when the surface of the polyurethane foam is subjected to film removal treatment and when it is not subjected to film removal treatment.

  When the reactive adhesive is a moisture curable adhesive, the laminated sponge of the present invention can be obtained after pressing, and can be manufactured at low cost. On the other hand, when the reactive adhesive is a thermosetting adhesive, the laminated sponge of the present invention can be obtained by further providing a drying step.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

1. Raw materials The materials used in the following examples and comparative examples are shown.
1-1. Polyolefin foam (1) Polyethylene foam (X1)
A plate-like polyethylene foam (closed cell structure) obtained by cutting “B-4” (trade name) manufactured by INOAC CORPORATION to a size of 1000 mm in length, 1000 mm in width and 30 mm in thickness was used. The apparent density is 0.027 g / cm ³ , the expansion ratio is about 37 times, and the 25% compression hardness is 0.050 MPa.
(2) Polyethylene foam (X2)
A plate-like polyethylene foam (closed cell structure) obtained by cutting “A-8” (trade name) manufactured by INOAC CORPORATION to a size of 1000 mm in length, 1000 mm in width and 30 mm in thickness was used. The apparent density is 0.062 g / cm ³ , the expansion ratio is about 16 times, and the 25% compression hardness is 0.090 MPa.

1-2. Polyurethane foam (1) Polyurethane foam (Y1)
A plate-like polyurethane foam (open cell structure) obtained by cutting “MF-80A” (trade name) manufactured by INOAC CORPORATION to a size of 1000 mm in length, 1000 mm in width and 10 mm in thickness was used. The apparent density is 0.075 g / cm ³ and the number of cells is 81/25 mm.
(2) Polyurethane foam (Y2)
A plate-like polyurethane foam (open cell structure) obtained by cutting “SC” (trade name) manufactured by INOAC CORPORATION to a size of 1000 mm in length, 1000 mm in width and 10 mm in thickness was used. The apparent density is 0.031 g / cm ³ and the number of cells is 40/25 mm.

1-3. Reactive Adhesive A reactive hot melt adhesive “4,4-diphenylmethane diisocyanate (MDI) -based moisture curable hot melt adhesive” (trade name) manufactured by Hitachi Chemical Co., Ltd. was used. Hereinafter, it is referred to as “reactive HM”.

1-4. Primer layer forming material “UXA3004A” (trade name) manufactured by Sanyo Chemical Industries, Ltd. was used.

2. Example 1 Production and Evaluation of Laminated Sponge
A metal flat plate having a heater heated to 400 ° C. was brought into contact with the surface of the polyethylene foam (X1), and the surface having a thickness of 0.5 mm was melted. Thereafter, when the molten surface (flat surface) of the polyethylene foam (X1) was at room temperature, a reactive adhesive was applied to the surface using a roll coater (coating amount 50 g / m ² ).
Next, the polyurethane foam (Y1) was brought into contact with the surface of the adhesive layer before the adhesive layer was cured. Then, using a compression press plate, when the total thickness of the polyethylene foam and polyurethane foam is 100%, compression is performed under the condition of a pressing time of 5 seconds while compressing to a thickness of 90%. The laminated body 1 in which the foam layer 11, the adhesive layer 12, and the polyurethane foam layer 13 were sequentially joined was obtained (see FIG. 1).
The obtained laminates were respectively immersed in the following cleaning agents and subjected to a T-type peel test according to JIS K6854-3. The results are shown in Table 1. Specific operation using each cleaning agent is shown below.
(1) Kerosene The laminate was immersed in kerosene for 24 hours, and when the polyethylene foam layer and the polyurethane foam layer were completely peeled off, it was judged as “complete peeling”. When there was no peeling of the adhesive surface, the above T-type peeling test was conducted, it was judged as “material destruction”, and the measured peeling strength was also shown.
(2) Wax for automobile “Mirror surface Wax coat” (trade name) manufactured by Wilson Co., Ltd. was used. This is a liquid wax containing wax, silicone, resin, petroleum solvent (about 25% by mass), fine particle powder (5% by mass) and the like.
When the laminate was immersed in this wax for 1 hour and the polyethylene layer and the polyurethane layer were partially peeled off (if they were adhered but peeled at the interface), it was judged as “partial peeling”. Also, if there is no peeling of the adhesive surface, it is judged as “material destruction”, the wax is removed by pressing, and after drying for 1 hour, the above-mentioned T-type peeling test is performed, and the measured peeling strength is also shown. did.
Thereafter, the same treatment was performed for another hour and the same evaluation was performed.
(3) Automotive Body Cleaner “Pitch Ippatsu!” (Trade name) manufactured by Linley was used. This is a liquid spray type cleaner containing silicone, hydrocarbon solvent (about 70% by mass) and the like.
When the laminate was immersed in this cleaner for 1 hour and the polyethylene layer and the polyurethane layer were partially peeled (if they were adhered but peeled at the interface), it was judged as “partial peeling”. If there is no peeling of the adhesive surface, it is judged as “material destruction”, the cleaner is removed by squeezing, and after drying for 1 hour, the above T-type peel test is performed, and the measured peel strength is also shown. did.

Example 2
A laminate is produced in the same manner as in Example 1 except that the polyethylene foam (X1) and the polyurethane foam (Y1) are used and the surface of the polyethylene foam (X1) is melted by a thickness of 1.0 mm. And evaluated (see Table 1).

Example 3
A laminate was produced and evaluated in the same manner as in Example 2 except that the polyethylene foam (X1) and the polyurethane foam (Y2) were used (see Table 1).

Example 4
A laminate was produced and evaluated in the same manner as in Example 2 except that the polyethylene foam (X2) and the polyurethane foam (Y1) were used (see Table 1).

Comparative Example 1
A laminate was manufactured and evaluated in the same manner as in Example 1 except that the heat treatment of the surface of the polyethylene foam (X1) was not performed (see Table 1).

Comparative Example 2
Except that polyethylene laminate (X1) and polyurethane foam (Y1) were used, and one side of each foam was melted and brought into full contact with each other to produce a laminate, the same as in Example 1. Evaluation was performed (see Table 1).

Comparative Example 3
Instead of heating and melting the surface of the polyethylene foam (X1), a laminate was produced and evaluated in the same manner as in Example 1 except that the primer layer forming material was applied (coating amount 40 g / m ² ). (See Table 1).

As is clear from Table 1, it can be seen that the laminates obtained in Examples 1 to 4 have excellent resistance to a cleaning agent, a polishing agent (wax or the like) containing an organic solvent, and the like. . Comparing Examples 1 and 2 using the same foams, Example 2 in which the thickness of the surface layer portion of the polyethylene foam (X1) melted by heating is larger has a higher peel adhesion, and the organic solvent It turns out that it is hard to receive the influence of the adhesive fall by.
On the other hand, Comparative Example 1 is an example in which the surface of the polyethylene foam (X1) was not heat-treated, and it can be seen that the solvent resistance is insufficient. Comparative Example 2 was an example of heat welding instead of using a reactive adhesive, which had resistance to kerosene and wax, but was not sufficient for a cleaner containing a large amount of organic solvent. . Comparative Example 3 is an example in which a primer layer is formed instead of performing heat treatment on the surface of the polyethylene foam (X1). The primer layer is resistant to kerosene and wax, but contains a large amount of an organic solvent. Not enough for the cleaner.

  The laminated sponge of the present invention can be used with cleaning agents containing organic solvents such as alcohol, toluene, hydrocarbon solvents, petroleum solvents, polishing agents (waxes, etc.), coating agents, and the like. And efficiently remove oil stains attached to the vehicle body, window glass, tires, wheels, outdoor display bodies (signboards, display devices, etc.), walls for houses and buildings, floors, glass, lattices, fences, etc. Cleaning, polishing, or contamination can be suppressed.

It is the schematic which shows an example of the cross-sectional structure of the laminated sponge of this invention.

Explanation of symbols

1; laminated sponge 11; polyolefin foam layer 12; adhesive layer 13; polyurethane foam layer

Claims (8)

  Heat-treated polyolefin foam layer, adhesive layer formed on the heat-treated surface of the polyolefin foam layer and cured using a reactive adhesive, and bonded to the surface of the adhesive layer A laminated sponge comprising a polyurethane foam layer sequentially.   The laminated sponge according to claim 1, wherein the polyurethane foam layer has been subjected to film removal treatment.   The laminated sponge according to claim 1 or 2, wherein the reactive adhesive is a urethane adhesive. The laminated sponge according to any one of claims 1 to ³ , wherein the polyolefin foam layer has a density of 0.020 to 0.070 g / cm ³ .   A heating step of heating the surface of the polyolefin foam to melt the surface layer portion; a coating step of applying a reactive adhesive to the heat-treated surface of the polyolefin foam to form an adhesive layer; and polyurethane foam A pressure-bonding step in which a body is brought into contact with the adhesive layer, and the polyolefin foam and the polyurethane foam are pressure-bonded. A method for producing a laminated sponge, characterized by bonding.   The method for producing a laminated sponge according to claim 5, wherein the polyurethane foam is subjected to film removal treatment.   The method for producing a laminated sponge according to claim 5 or 6, wherein the reactive adhesive is a urethane adhesive. The method for producing a laminated sponge according to any one of claims 5 to 7, wherein the polyolefin foam has a density of 0.020 to 0.070 g / cm ³ .

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