WO2008047402A1

WO2008047402A1 - Sheet elastomer

Info

Publication number: WO2008047402A1
Application number: PCT/JP2006/320586
Authority: WO
Inventors: Tadashi Sato
Original assignee: Inoac Corporation; Rogers Inoac Corporation
Priority date: 2006-10-16
Filing date: 2006-10-16
Publication date: 2008-04-24
Also published as: CN101678614A; KR20090098785A; KR101324019B1; JPWO2008047402A1

Abstract

A sheet elastomer that is capable of simultaneously exhibiting scratch resistance and sealing capability by good flexibility and elasticity. There is provided a sheet elastomer comprised of sheetlike elastic foam substrate (12) as required, wherein the entirety of one surface (12a) along the thickness of the sheetlike elastic foam substrate (12) is covered with resin composition (R) as required, and wherein in a surface layer portion of the surface (12a), the resin composition (R) is present in cells (28) partitioned by foam skeleton (13) constituting the sheetlike elastic foam substrate (12), and wherein in the surface layer portion of the surface (12a), there is created resin composition presence region (14) resulting from integration of the sheetlike elastic foam substrate (12) and the resin composition (R).

Description

Specification

Sheet elastic body

Technical field

The present invention relates to a sheet-like elastic body, and more particularly to a sheet-like elastic body suitably used as a sealing material such as a gasket or packing for electronic equipment and precision equipment.

Background art

[0002] In a display or the like of a general household appliance, a mobile phone, or a portable information terminal, for example, a device such as a liquid crystal display unit is disposed so as to face the outside of the casing. In such devices, for example, a seal member is interposed between the casing and the peripheral edge of the casing to prevent dust prevention, light leakage of the knocklight, rattling, and the like. As such a sealing member, a polyurethane foam which is easily deformed at a low load as described in Patent Document 1 and in which a film material is integrally formed on one side has been reported.

Patent Document 1: Japanese Patent Laid-Open No. 2001-100216

[0003] By the way, with the recent improvement in function and weight reduction required for cellular phones and the like, the above-described required characteristics for seal members have also been advanced. This has been achieved by improving the functions of ICs used, increasing the degree of material integration by unifying the IC sizes, saving space by introducing large-scale LSIs, and stacking multiple substrates. When a large number of parts are integrated in this way, the structure and the fitting structure of the housing become complicated. In order to cope with this, a sealing member has been devised that ensures a sufficient sealing performance in a wide and compressive range within the same thickness as described in Patent Document 2.

Patent Document 2: Japanese Patent Laid-Open No. 2005-227392

Disclosure of the invention

Problems to be solved by the invention

[0004] In the invention described in Patent Document 2, while the sealing property is good, the scratch resistance is low due to flexibility. For this reason, if the handling is rough, there is a problem that the seal member is easily damaged. This damage can be caused by poor sealing performance or small pieces from the damaged seal member. For example, it causes secondary problems that remain on the LCD screen and reduce the product value.

[0005] In view of the above-described problems inherent in the sheet-like elastic body according to the prior art, the present invention has been proposed to suitably solve these problems, and has a sealing property due to good flexibility and elasticity. Another object is to provide a sheet-like elastic body that can have both scratch resistance and scratch resistance.

Means for solving the problem

[0006] In order to overcome the above-mentioned problems and achieve the intended purpose, a sheet-like elastic body of the present invention is a sheet-like elastic body comprising a sheet-like elastic foam substrate,

The entire one surface in the thickness direction of the sheet-like elastic foamed substrate is covered with the resin composition,

In the surface layer portion of the surface, the resin composition is present in a cell defined by a foam skeleton constituting the sheet-like elastic foam substrate,

Thus, the gist of the present invention is that a resin composition existing region in which the sheet-like elastic foamed substrate and the resin composition are combined is formed in the surface layer portion.

[0007] Therefore, according to the invention of claim 1, it is possible to maintain low hardness even under high compression, exhibit suitable sealing properties under a wide and compressed state, and exhibit scratch resistance.

[0008] The invention according to claim 2 is the invention according to claim 1, and in the region where the resin composition is present, the resin composition and the foam skeleton are fused at the contact site. It is necessary to do so.

Therefore, according to the invention of claim 2, it is possible to maintain low hardness even under high compression, exhibit suitable sealability under a wide range of compression conditions, and exhibit scratch resistance.

[0009] The invention according to claim 3 is the invention according to claim 1 or 2, wherein the region where the resin composition is present is based on JIS K 7218 when the material of the contact pressing body is (1) stainless steel. (2) Load is 1.2kg, and (3) The evaluation is carried out under the condition of 43 rotations and 43 rotations.

Therefore, according to the invention of claim 3, sufficient scratch resistance is ensured.

[0010] In order to overcome the above-mentioned problems and achieve the intended purpose, a sheet-like shape according to another invention of the present application The elastic body has a sheet-like elastic foam substrate having a sheet-like elastic foam substrate, and the sheet-like elastic foam substrate has a 50% compression load of 0.025 MPa or less and a 75% compression load of 0.40 MPa or less.

As a result, the sheet-like elastic foam substrate and the resin composition are combined on the surface layer portion of the surface, and based on JIS K 7218, the material of the contact pressing body is (1) stainless steel, 2) The load is 1.2kg, and (3) the presence of a resin composition region with a resistance of 10 rotations or more is evaluated based on the evaluation carried out under the condition of 43 rotations and Z rotations. To do.

[0011] Therefore, according to the invention of claim 4, low hardness can be maintained even under high compression, and suitable sealability can be expressed under a wide range of compression, and scratch resistance can be expressed.

[0012] The invention according to claim 5 is the invention according to any one of claims 1 to 4, wherein the thickness of the resin composition existing region is in the range of 1 to 25 m. The gist.

Therefore, according to the invention of claim 5, it is ensured that low hardness is maintained under high compression and sufficient scratch resistance is exhibited.

[0013] The invention according to claim 6 is the invention according to any one of claims 1 to 5, wherein the tensile strength of the resin composition according to JIS K 6251 is in the range of 1.0 to 80 MPa. This is the gist.

Therefore, according to the invention of claim 6, sufficient scratch resistance is ensured.

[0014] The invention according to claim 7 is the invention according to any one of claims 1 to 6, wherein the elongation defined in JIS K 6251 in the substance constituting the resin composition existing region is the The gist is that the elongation of the single-walled coasting foam substrate exceeds the elongation specified in JIS K 6251.

Therefore, according to the invention of claim 7, sufficient scratch resistance is ensured.

The invention's effect

[0015] According to the sheet-like elastic body according to the present invention as described above, it is possible to produce a sheet-like elastic body that maintains low hardness under high compression and has sufficient scratch resistance.

Brief Description of Drawings FIG. 1 is a cross-sectional view showing the internal structure of a sheet-like elastic body according to a preferred embodiment of the present invention.

FIG. 2 is a process diagram showing a method for producing a sheet-like elastic body according to an example.

FIG. 3 is a schematic view showing an example of a sheet-like elastic body manufacturing apparatus according to an embodiment.

FIG. 4 is a cross-sectional view showing a film for transferring a resin composition according to an example.

FIG. 5 is a cross-sectional view showing a film for transferring a resin composition having a two-layered resin composition region.

[Fig. 6] Schematic representation of states in each step such as an elastic foam substrate raw material, a sheet elastic foam substrate, a resin composition existing region, and a substrate film used when producing a sheet-like elastic body according to an example. FIG.

FIG. 7 is a cross-sectional view showing the internal structure of a sheet-like elastic body according to a modified example.

FIG. 8 is a schematic view showing an apparatus for producing a sheet-like elastic body according to a modified example.

FIG. 9 is a schematic view showing an apparatus for producing a sheet-like elastic body according to another modification.

FIG. 10 is an overall schematic diagram showing a test apparatus used for evaluation of scratch resistance carried out in Experiments 1 to 3.

BEST MODE FOR CARRYING OUT THE INVENTION

[0017] Next, the sheet-like elastic body according to the present invention will be described below with reference to the accompanying drawings by way of preferred examples. The inventor of the present application has a resin composition in which the base and the required resin composition are integrated with a surface layer portion on one surface of a sheet-like elastic foamed substrate that can ensure sufficient sealing performance with a small thickness. It has been found that by forming a physical region, a sheet-like elastic body that does not impair the physical properties of the substrate and achieves the required scratch resistance can be obtained. This sheet-like elastic body is suitably used for a housing fitting portion of a mobile phone or the like, and prevents an increase in sealing performance and non-ringing performance and low commercial value due to damage. Here, the physical properties of the sheet-like elastic foam substrate are: (A) 50% compressive load (hereinafter referred to as 50% CLD) and 75% compressive load (hereinafter referred to as 75% CLD), each of which is a certain value or less. Or (B) —the density below a certain value. These (A) and (B) are both indicators for achieving low hardness under high compression conditions in the present invention. One surface refers to the surface on the side that receives rubbing or the like due to the fitting of the housing or the like. In the present invention, “cell “The presence of the rosin composition in the inside” means a state in which the rosin composition has entered at least a part of the cell. And “the resin composition and the foam skeleton are fused at the contact site” means that the resin composition and the foam skeleton are mixed and integrated by eliminating the boundary due to compatibility. Point to.

[0018] The scratch resistance evaluation of the present invention is basically performed based on JIS K 7218.

In this evaluation, (1) the material of the contact pressing body is stainless steel, (2) the load is 1.2 kg, and (3) the rotation speed is 43 rotations Z (details will be described later [0027]: evaluation below) It is called a condition.) In this evaluation, having durability means that there is no visible scratch on the side of the sheet-shaped elastic body where the resin composition is present at the end of the constant rotation performed under the evaluation conditions! Point to. In the present invention, from the knowledge obtained from Experiment 1 (described later), the boundary for judging the scratch resistance is 10 rotations under the evaluation conditions. In other words, if there were no problems with the sheet-like elastic body that was the evaluation object after 10 revolutions, it was judged that the sheet-like elastic body had scratch resistance.

A sheet-like elastic body 10 according to an embodiment includes (a) a sheet-like elastic foam substrate (hereinafter simply referred to as a substrate) 12 and a surface layer portion on one surface 12a of the substrate 12 as shown in FIG. (B) the resin composition existing region 14 and the other surface (back surface) of the substrate 12 opposite to the resin composition existing region 14 (c) the substrate film 18 And basically consists of Here, (a) the substrate 12 achieves the required flexibility and sealing properties, and (b) the resin composition existing region 14 is the foam skeleton 13 and the resin composition (hereinafter referred to as the resin composition) that define the cells 28. (Simply referred to as a composition) In the region where R is integrated, the required scratch resistance is exhibited. (C) The base film 18 plays a role of improving the structural strength of the sheet-like elastic body 10 respectively. . The integration of the foam skeleton 13 and the composition R means that the composition R exists in (enters) the cell 28 and is in contact with the foam skeleton 13 that defines the cell 28. It refers to the state of fusion. Here, the state in which the composition R exists only in the cell 28 and the foam skeleton 13 and the composition scale are not fused together is included. The composition R is partially in the cell 28 in the surface layer portion of the surface 12a.

[0020] The substrate 12 is preferably manufactured based on a well-known mechanical calfloss method. In other words, an elastic foam substrate material (hereinafter simply referred to as “raw material”) in which a predetermined amount of foam-forming gas is mixed with a resin material consisting of polyol and isocyanate as main materials and a foam stabilizer as a secondary material. It is manufactured by continuously supplying M to the base film 18 that is also used as a transfer medium in the manufacturing process (described later) and controlling the thickness. The mecha-calfloss method is described in detail, for example, in Japanese Patent Publication No. 53-8735. The foam has a semi-self foam structure in this embodiment. In addition, the substrate 12 is a known material that has less material and less gas generation and has flexibility and followability to a curved surface so as to maintain functions such as dust prevention and light leakage prevention over a long period of time. Substances, such as synthetic resin foams, are preferred. Specific examples include foams made from various types of resin such as urethane, polystyrene, silicone, talyl or polychlorinated bur, or various rubbers such as NBR, SBR, EPDM or EPM.

[0021] The density of the substrate 12 is in the range of 50 to 250 kg / m ³ . By setting it in this range, even if the rosin composition existing region 14 is formed in the surface layer portion on the surface 12a, a sufficiently low hardness can be maintained in a high compression state. If this value exceeds 250 kg / m ³ , the hardness will increase and the sealing performance will deteriorate. The lower limit of density varies depending on the production method (described later). Substrate 12 Ca force - when produced by Karufurosu method, lOOkg / m ³ is the lower limit. If it is less than lOOkg / m ³ , the foaming gas is not uniformly mixed with the raw material of the resin, and the bubbles forming the cells 28 are not stably maintained, causing problems such as cell roughening and voids. This is because the expression of sealing properties is inhibited. When the mecha-calfloss method and the chemical foaming method are used in combination, 5 Okg / m ³ is the lower limit. However, if it is less than 50 kg / m ³ , the bubbles forming the cell 28 are not stably maintained. The thickness of the substrate 12 is preferably in the range of 0.3 to 5.0 mm. This lower limit is a numerical value for ensuring sufficient sealing performance under high compression. On the other hand, the upper limit is a numerical value derived empirically from use in devices that require space saving, such as mobile phones.

[0022] The properties of the sheet-like elastic body achieved by this density and thickness can be expressed by 50% CLD and 75% CLD. In this case, the numerical values are 0.025 MPa or less and 0 • 40 MPa or less, respectively. 50% CLD and 75% CLD are sheet-like elastic bodies that are required to cover 50% and 75% physical compression, respectively, that is, 50% and 75% physical compression. 10 represents the hardness as a whole. If this value exceeds the above-mentioned value, it is too hard and the flexibility to physical compression is poor, and sufficient sealability cannot be achieved. More The load on the case becomes large, and the case may be distorted, cracked, chipped and other physical defects during use. This hardness is basically the numerical value of the substrate 12. However, in the present invention, the resin composition existing region 14 is formed in the surface layer portion on the surface 12a, and the composition R and the substrate 12 are inseparably integrated to form an inseparable structure. The numerical value of the entire body 10 is the same.

In addition, the diameter of the cell 28 of the substrate 12 is set to 500 μm or less, preferably 300 μm or less in order for the sheet-like elastic body 10 to exhibit a suitable sealing property. If this value exceeds 00 μm, the dustproofness and light-shielding properties will decrease. In particular, in order to sufficiently achieve the performance required for recent precision instruments, 300 m or less is preferable. That is, in the case of 300 to 500 / ζ πι, although there is no problem in dustproofness, slight light leakage may occur depending on the light source intensity. Further, since the sheet-like elastic body 10 according to the present embodiment is manufactured mainly by the mechano-calf floss method, the surface is provided with a skin layer unless post-processing is performed. This can structurally improve the adhesion to the object to be sealed.

[0024] The raw material of the base 12 constituting the sheet-like elastic body 10 having such physical properties basically conforms to the contents described in Japanese Patent Publication No. 53-8735. In order to keep the density and the like in the above-mentioned range, the mixing ratio of the foaming gas to 100 parts by volume of the resin raw material composed of the main raw materials polyol and isocyanate and the auxiliary raw material foam stabilizer is 300 volume% or more. Is done. If this is less than 300% by volume, the density of the sheet-like elastic body 10 will not be less than 250 kg / m ^3, and the sealing performance when a high compression rate is obtained cannot be ensured. When the chemical foaming method is used in combination, a foaming agent, a surfactant, a catalyst for delaying the curing of the substrate 12 under control, and the like are used as auxiliary materials.

[0025] The resin composition existing region 14 is basically an area where the composition R enters the cell 28 (void) in the surface layer portion of the surface 12a of the substrate 12, or the region where the composition R enters, This is a region where the boundary with the foam skeleton 13 disappears due to solubility and is fused and integrated (see Fig. 1) .o This fusion makes the composition R inseparable from the substrate 12 and a single layer. As shown in FIG. Therefore, the presence of the resin composition existing region 14 does not deteriorate the physical properties related to the flexibility of the substrate 12. [0026] As the composition R, a required resin, preferably a material similar to that of the substrate 12, such as a urethane resin, is used. In addition, known substances such as acrylic resins, polyesters, bulls, epoxies, polyamides, polystyrenes, various synthetic resins, and various synthetic rubbers may be used singly or in combination. The composition R is required to have a tensile strength in the range of 1.0 to 80 MPa in accordance with JIS K 6251. This ensures the flexibility of the sheet-like elastic body 10 according to the present invention and the scratch resistance of the surface 12a. That is, when the tensile strength is less than 1.0 MPa, the scratch resistance is not satisfied. On the other hand, if it exceeds 80 MPa, the flexibility of the sheet-like elastic body 10 as a whole is poor. Further, a substance having an elongation larger than the elongation of the substrate 12 ([IS K 6251) and having high compatibility with the material of the substrate 12 is preferably selected. The elongation is 50% or more, preferably 100% or more, compared to the material of the substrate 12 described above. Regarding the compatibility, it is preferable that the difference between the solubility parameters is 1.0 or less. By using such a rosin or the like as a material, the following effects can be obtained. In other words, at the time of manufacturing, (i) it is possible to improve the familiarity when forming the resin composition existing region 14 on the substrate 12 to facilitate fusion. In addition, during use, the integral retention property (followability) of the resin composition region 14 to the substrate 12 is ensured.

[0027] The composition R is required to exhibit plastic flow during the production (heating) of the sheet-like elastic body 10. Here, the plastic flow refers to a flow in which each molecule constituting the polymer composition R enters the surface layer portion of the surface 12a only at a temperature equal to or higher than the glass transition point. Such a plastic flow state is distinguished from a flow state that occurs at a melting temperature or higher. That is, the composition R that is not in a plastic flow state and remains in a glass state even when heated is not suitable because it does not enter the cell 28. In addition, the composition R that becomes fluidized at a temperature equal to or higher than the melting temperature and decreases in viscosity penetrates the entire substrate 12. For this reason, the composition R is not preferred because it cannot form the resin composition existing region 14 in the surface layer portion of the surface 12a and deteriorates physical properties such as hardness of the sheet-like elastic body 10. The composition R that plastically flows as described above can be completely melted by, for example, a crosslinked type of resin that exhibits a certain fluidity without being melted by heat, or by heating when the sheet-like elastic body 10 is manufactured. However, a thermoplastic resin is preferred. By using a substance that achieves this condition, a surface 12a that develops a plastic flow state and does not adversely affect the physical properties of the substrate 12a. Thus, a sheet-like elastic body 10 in which the composition R is formed on the surface layer portion thereof can be produced.

[0028] The resin composition region 14 has a thickness in the range of 1 to 25 μm, preferably 2 to 20 μm, and more preferably 3 to 10 m. Here, the thickness is the thickness of the portion where the substrate 12 and the composition R are integrated, and represents the depth from the surface 12a to the position where the composition R exists (D in FIG. 1 or FIG. 7). reference). If the thickness is less than 1 m, sufficient scratch resistance cannot be obtained. On the other hand, if it exceeds 25 m, the sealing properties and cushioning properties of the sheet-like elastic body 10 itself are impaired. This numerical range of thickness is derived based on knowledge obtained from Experiment 1 described later. In other words, in the range of 3 to 10 / ζ πι, there is no problem in scratch resistance at the end of 100 revolutions under the evaluation conditions, and the followability is good. Also, in the range of 2 to 3 / ζ πι or 10 to 20 m, 30 revolutions in the evaluation conditions (without the rosin composition existing region 14 and in the conventional sheet-like elastic body 10 in which a small scratch of less than 5 mm was confirmed. The number of revolutions, which becomes the boundary region, was at a level where there was no problem with scratch resistance at the end and no problem with follow-up.

[0029] It should be noted that the scratch resistance required for the resin composition existing region 14 is evaluated under the required evaluation conditions in the present invention. This evaluation condition is derived from the experimental result force of the conventional sheet-like elastic body 10 in Experiment 1 (described later), and has the accuracy to determine the limit under actual use. Specifically, the actual physical contact with the sealed member depends on external factors such as vibration and drop applied during product assembly (after product assembly or after product assembly) or product configuration. This is a condition that allows for the reproduction of the contents that can be qualitatively and quantitatively evaluated under more severe conditions, considering the contact situation. In other words, if there is no problem with this evaluation condition, it can be assumed that there is no problem even under actual use.

The base film 18 is a member that is integrally laminated on the base 12 that improves the structural strength of the sheet-like elastic body 10. It also serves as a transport medium for the raw material M as described in the manufacturing method (described later). Therefore, the material of the base film 18 has physical strength capable of resisting the tension applied during manufacture and resistance to heat that reacts and cures the raw material M. For example, heat shrinkage such as polyethylene terephthalate (PET). The use of various small resins is preferred. The other details are the same as those described in [Patent Document 2].

[0031] (About manufacturing apparatus and manufacturing method) Next, an apparatus for manufacturing a sheet-like elastic body according to the present embodiment and a manufacturing method using the apparatus will be described. The raw material M and the resin composition transfer film (hereinafter simply referred to as transfer film) 20 (described later) are prepared. The sheet-like elastic body 10 is basically subjected to the raw material preparation process Sl shown in FIG. Manufactured by the manufacturing apparatus 30 shown in FIG. The manufacturing apparatus 30 continuously performs the aforementioned steps S2 to S5, and the raw material preparation step S1 is separately performed in the mixing unit 31. Note that the raw material preparation step S1 is a step of preparing the transfer film 20 by preparing the raw material M of the substrate 12 by an appropriate conventionally known method. The details of the preparation of the raw material M and the detailed description of the manufacturing apparatus 30 are the same as in [Patent Document 2], and are therefore omitted.

[0032] (Film composition transfer film)

The transfer film 20 prepared in advance has a structure shown in FIG. In this embodiment, the layered product 15 is formed on the prepared transfer film 22 via the applied release agent 17. The layered product 15 is the composition R having a required thickness by a known gravure coater or the like. The coater to be used is appropriately selected depending on various conditions such as the thickness of the layered product 15 and the viscosity of the composition R. Here, the release agent 17 enhances the peelability of the layered product 15 from the transfer film 22. For example, known substances such as silicones, polyolefins, melamines, epoxies, ethylene vinyl acetates, and vinyl chloride vinyl acetates or vinyl acetates are appropriately selected in the form of a single substance or a mixture of several kinds. . The transfer film 22 has a physical strength capable of resisting the tension due to the resin composition existing region application mechanism (hereinafter simply referred to as an application mechanism) 35 and resistance to heat that causes the raw material M to react and cure. In addition, various resins having a smooth surface, such as PET and having a small thermal shrinkage, are preferably used.

In this example, the layered product 15 is a single layer, but the present invention is not limited to this. As shown in FIG. 5, a second layered material 15b having a required thickness is formed from the second composition R2 on the transfer film 22 provided with the release agent 17, and the first composition is formed thereon. A multi-layer structure in which R1 is applied to form the first layered material 15a having a required thickness may be used. In this case, by using a material that is compatible with both the base 12 and the second layer 15b as the material of the first layer 15a, the base 12 and materials that are not in contact with each other can be selected as the respective materials of the second layered material 15b. For example, (ii) Scratch resistance is used as the material of the second layered material 15b on the outside, and, for example, glossy acrylic resin is used, and (mouth) the substrate 12 is excellent in flexibility and the like. In the case of using polyurethane foam, a material having compatibility with both of them, such as urethane, acrylic, polyester, polyamide, or various synthetic rubbers, is preferably employed as the first layered product 15a. In this case, the sheet-like elastic body 10 having suitable flexibility, scratch resistance and surface gloss can be obtained. Of course, the layered material 15 may have a structure of three or more layers as required.

[0034] When the layered product 15 has two or more layers, a substance that expresses a required function (hereinafter referred to as a functional material) F is mixed with the composition R, and this function is added to the sheet-like elastic body 10. Can be granted. This uses composition R as a binder and imparts a specific function. Specifically, the second composition R2 force in which the functional substance F is mixed is also formed on the transfer film 22 through the release agent 17 to form the second layered material 15b, and the first composition is further formed thereon. The force of the object R1 is also generated by forming the first layered object 15a (see FIG. 5).

By the way, the mixing of the functional substance F does not affect the surface physical properties such as scratch resistance, but deteriorates the volume physical properties such as tensile strength. For this reason, when the layered product 15 is a single layer, it is difficult to apply, and there arises a problem that the layered product 15 is partially peeled off from the transfer film 22 even if it is lightly touched by an operator. This problem is particularly fatal in a state where the thickness is thin (<25 m or less) and the material is not substantially bonded to another substance via the release agent 17 (see FIG. 4). However, if the layered product 15 has two or more layers, a so-called anchor effect appears between the first layered product 15a and the second layered product 15b, and this problem can be avoided. The same effect can be obtained when the functional substance F is mixed with either the first composition R1 or the second composition R2.

It should be noted that the transfer film 20 shown in FIG. 4 and FIG. 5 is used in a form in which the upper and lower sides are interchanged when applied to the raw material M by the manufacturing apparatus 30 in a stacked manner. In FIG. 5, the second layered material 15b mixed with the functional substance F is located on the transfer film 22 side, but the present invention is not limited to this. That is, the functional substance F is mixed with the first composition R1 to form the first layered product 15a containing the functional substance F, and this is formed into the second layered product 15b. It may be protected in a covering manner. In this case, a direct protective action is also added by the covering only by the anchor effect. In this way, when the layered product 15 is formed as a multi-layer, it is preferable that the thickness is: L m or more in consideration of the bonding properties of both layers. If this value is less than 1 μm, the above-mentioned anchor effect and covering protection effect are insufficient. The functions imparted by the functional substance F include all the characteristics imparted by substances such as known powders that can be mixed with the binder, such as coloring, hygroscopicity, electrical conductivity or electromagnetic shielding properties. It is done. In addition, since the first layered material 15a and the second layered material 15b formed as a multilayer are integrated with each other by heating, the resin composition existing region 14 is formed in the same manner as the single-layered layered product 15. Form.

[0037] The manufacturing apparatus 30 shown in FIG. 3 basically conforms to the manufacturing apparatus described in [Patent Document 2]. In other words, the roll mechanism 32 (feed roll 32a and product collection port 32b) that drives the base film 18, the discharge nozzle 34 that supplies the raw material M onto the film 18, and the downstream of the raw material M with a predetermined thickness. The product thickness control means 36 and the downstream heating means 38 are provided. The discharge nozzle 34 supplies the raw material M as shown in FIG. 6 (a) onto the base film 18 under control, and one end thereof is connected to the mixing unit 31 that performs the raw material preparation step S1. . The product thickness control means 36 functions as a roll that applies the raw material M as shown in FIG. 6 (b) to the required thickness and also applies the transfer film 20 to the raw material M in a stacked manner. Various blades may be adopted as the product thickness control means 36 so as to be independent from the applying mechanism 35. A supply roll 35a and a transfer film collection roll 35b for driving the transfer film 20 for applying the layered material 15 to the upper side of the raw material M are disposed upstream and downstream of the product thickness control means 36, respectively. An application mechanism 35 is configured. The imparting mechanism 35 is a mechanism that supplies the production line while applying tension to the transfer film 20 and collects only the transfer film 22. Here, the wound transfer film 20 is sent out from the supply roll 35a under control. By passing through this part, the raw material supply 'resin composition application step S2 is completed, and after passing through the transfer film recovery roll 35b located on the downstream side of the heating means 38, the transfer film removal step S4 (Fig. 6 (c) Reference) is completed.

[0038] In the heating means 38, the raw material M is heated under reaction to be reacted and cured to form the substrate 12, and at the same time, the resin composition in which the layered product 15 (composition R) and the substrate 12 are integrated. Existence region 14 formed Is done. Here, the unity of the layered product 15 and the substrate 12 is very strong due to the change of the layered product 15 itself into a plastic flow state, the adhesion effect, and the reaction'curing of the raw material M. . Further, the base film 18 is firmly bonded to the substrate 12 and laminated integrally by the reaction effect of the raw material M by heating and the adhesive effect by curing. The heating temperature by the heating means 38 is set to a temperature range in which the layered product 15 changes to a plastic flow state. Specifically, the temperature is about 150 to 200 ° C. where the raw material M can be reacted and cured by heating. Then, the heating step S3 is completed by passing through the heating means 38.

[0039] The final step S5 is a step of obtaining a long object of the sheet-like elastic body 10 basically through the steps S1 to S4 so far. If necessary, it is punched into the final seal material shape that is the final product, and a final inspection is conducted. In addition, the sheet-like elastic body 10 may be shipped in a form in which the final inspection is performed and the product collection roll 32b is wound up and collected. In this case, the sheet-like elastic body 10 is continuously manufactured as a long object, and the manufacturing cost can be greatly reduced. In the production of the sheet-like elastic body 10, on the raw material M side of the transfer film 20, a melting point of 60 to 150 ° C., for example, a hot melt type such as polychlorinated butyl, polyacetic acid butyl, polyolefin or acrylic resin, etc. This adhesive may be applied by a known means such as spray coating. Since this adhesive is cured through the heating step S3, the unity between the substrate 12 and the layered product 15 (composition R) can be further strengthened. Here, if the melting point is less than 60 ° C, there is a risk of causing adverse effects such as blocking in high temperature production such as in summer. On the other hand, if it exceeds 150 ° C, it will not melt in the heating step S3, and a sufficient adhesive effect cannot be expected. In addition, a pre-manufactured base 12 or a commercially available product may be used as the base 12.

[0040] In addition, it is also possible to manufacture by using the above-mentioned mechanical floss method and chemical foaming method in combination. In this case, a chemical foaming agent is used as an auxiliary material for the raw material M. As the (chemical) foaming agent, water is particularly mentioned, and a surfactant or catalyst suitable for this foaming agent may be used in combination with various auxiliary materials suitable for the conventional mechanical calf froth method. Especially by selecting the catalyst

It is preferred to control the curing reaction of M and it is used at 0.1 to 8% by weight of the total amount of the main raw material in raw material M. In addition, (chemical) blowing agents include azo compounds, substituted hydrazines, semicarbazides, triazoles, benzoxazines or sodium carbonate. A mixture of citric acid is used. The amount of this blowing agent is adjusted according to the drug and the desired foam density, and is usually 0.1 to LO weight percent of the total amount of the main ingredients in ingredient M. One or several physical foaming agents may be used in combination with the above (chemical) foaming agents. Examples of the physical foaming agent include hydrocarbons such as fluorocarbons, fluoroethers and pentane, ethers and esters. Further, materials containing partially halogenated hydrocarbons, ethers or esters are also included. Typical physical blowing agents have boiling points of 50 to: LOO ° C. The physical foaming agent is used in an amount sufficient to give a desired bulk density to the obtained foam, usually 5 to 50% by weight of the total amount of the main raw material in the raw material M. In one embodiment, water ((aerologic) blowing agent) is used with one or more physical blowing agents.

[0041] Examples of the catalyst include organic acids of bismuth, lead, tin, iron, antimony, uranium, cadmium, cobalt, trim, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, mangan or zirconium. Examples thereof include salts, inorganic acid salts or organometallic derivatives, phosphines or tertiary organic amines. In particular, iron (metal) acetyl ether toner KFeAA) is preferred because of its stability, good catalytic activity and non-toxicity. By adding acetylethylacetone (2,4 pentanedione) to this FeAA, it is possible to provide an effect of avoiding premature curing at low temperatures and a high catalytic effect when heated by the heating means 38. Here, the weight ratio of FeAA to acetylacetone is 2: 1, and the amount of catalyst present in the reactive composition is 0.03 to 3.0% by weight based on the weight of the active hydrogen-containing component. A surfactant such as an organic silicone surfactant may be used for the purpose of stabilizing the raw material M (substrate 12) before curing. The preferred molar ratio of silicate unit to trimethylsiloxy unit is 0.8: 1 to 2.2: 1. In addition, conventional organic polysiloxane polyoxyalkylene block copolymers can be used. In addition, fillers (alumina trihydrate, silica, talc, calcium carbonate, clay or magnesium hydroxide), dyes, pigments (for example, titanium dioxide and iron oxide), antioxidants, antiozonants, difficult Any commonly used additive such as a flame retardant, UV stabilizer, conductive filler, and conductive polymer may be added to the raw material M.

[0042] (Modification example) In the above-described embodiment, the base film 18 is laminated on the sheet-like elastic body 10 to improve the structural strength and improve the handleability of the product. However, this does not exist in the present invention, and specifically, it may be in the form of a sheet-like elastic body 24 shown in FIG. The sheet-like elastic body 24 is manufactured by, for example, a manufacturing apparatus 50 shown in FIG. The manufacturing apparatus 50 has the same structure as the manufacturing apparatus 30 except that the roll mechanism 32 includes a supply roll 32a, a product recovery roll 32b, and a base film recovery roll 32c. The recovered base film 18 may be reused.

[0043] (Another modification)

In addition, the sheet-like elastic body 24 may be manufactured by using the manufacturing apparatus 60 shown in FIG. 9 and reversing the positions of the base film 18 and the transfer film 20 in the manufacturing apparatus 30. In this case, the surface protective film 19 is used instead of the transfer film 20 in order to form the sheet by controlling the thickness while pressing the raw material M from above to prevent surface roughness. Further, the transfer film 20 is wound around the supply roll 32a provided in the roll mechanism 32, and the base film recovery roll 32c is used as a transfer film recovery roll. Further, instead of the applying mechanism 35, a surface protective film roll mechanism 37 for supplying the surface protective film 19 by the supply roll 37a and recovering the surface protective film 19 by the surface protective film recovery roll 37b on the downstream side of the heating means 38 is disposed. Is done. That is, the raw material M is formed in a state where it is sandwiched from above and below by the transfer film 20 as the transfer medium and the surface protection film 16. The transfer film 22 may be recovered and reused.

[0044] Further, in the case of manufacturing a sheet-like elastic body by using both the mechano-calf froth method and the chemical foaming method according to another example of modification, the use of the surface protective film 19 enables the above-mentioned raw material M In addition to preventing surface roughness due to pressing from above, it is possible to more efficiently lower the density of the sheet-like elastic body by preventing the scattering of gas generated by the chemical foaming method. In each example described above, the sheet-like elastic bodies 10 and 24 are continuously manufactured, but the present invention is not limited to this. For example, the transfer film 20 mm or the base film 18 having a length of about 5 m may be used, and the raw material M may be supplied and heated in batches.

[0045] (Experimental example)

Below, the sheet-like elastic body according to the present invention was evaluated for scratch resistance and the like. An experimental example is shown.

[Experiment 1] Scratch resistance of sheet-like elastic body

Prepare a sheet-like elastic body (manufacturing method is described below) that can be used only by the sheet-like elastic foam substrate according to each of the measurement examples 1 to 7 having the physical properties shown in Table 1 below. This is a circular shape with a diameter of φ 50 Χ 1.0πιπι. It was obtained by covering the sheet-like test piece S. Then, this test piece S was installed in a test apparatus 80 as shown in FIG. 10, and based on JIS Κ 7218 ([IS K 7218 quasi-base), (1) the material of the contact pressing body 82 was stainless steel, (2) Scratchability was evaluated under the conditions of a load of 1.2 kg, (3) 43 revolutions Z minutes (rotation speed 50 mmZsec) or 86 revolutions Z minutes (rotation speed lOOmmZsec). Scratch properties were evaluated from 10 to: L After rotating 10 rotations up to 00 rotation, remove the test piece S from the test device 80 and visually check the appearance. ○: No scratch, small scratch (Less than 5 mm), X: Scratch (5 mm or more) was evaluated in three stages. The materials used are as follows. The rotational speed represents the speed at which a point arbitrarily set on the outer edge of the test piece S moves by rotational movement.

[0047] (Method for producing sheet-like elastic body (sheet-like elastic foam substrate))

'Symbol A series and B (by mecha-calfloss method)

General-purpose polyether polyol 100 parts, Cross-linking agent (1,4 butanol) 3 parts, Thickener (hydroxide aluminum) 20 parts, Metal catalyst (stannas octoate) 0.1 part, Foam stabilizer (trade name SZ— 1940 (Silicone: Toray Dow) 5.0 parts. Next, the foaming gas calculated to reach the target density under the condition of 0.1. INLZsec, and the polyisocyanate set so that the isocyanate index is 0.9 to L.1. (Crude MDI, NCO content: 31%) is mixed to obtain an elastic foam substrate raw material. And according to the manufacturing method mentioned above, the sheet-like elastic body was manufactured from the elastic foam base material.

• Symbols C and D (Mecha-Calfloss method + Chemical foaming method)

Basically, 0.5 parts of water as a foaming agent is added as a force raw material in the same manner as the above-mentioned symbol A series and B mecha-calfloss method (the required amount of foaming gas is added to the mixture of symbol A series). Symbol C) is a mixture of water and water, and symbol D) is a mixture of water and symbol B.

[table 1] Elongation Tensile strength

No.12 material

(%) (MPa)

Measurement example 1 A P U 400 140 0.20

Measurement example 2 A '240--Measurement example 3 A "150 155 0.10

Measurement example 4 Α '"100--Measurement example 5 Β 240 160 0.13

Measurement example S C 100 170 0.05

Measurement example 7 D 80 50 0.12

. In Table 1, the elongation and tensile strength conform to JIS K 6251.

It is a measured value.

• In Table 1, P U represents polyurethane.

[0048] (Result of Experiment 1)

The results are shown in the following Table 2 ((a) is for 43 revolutions per minute Z and (b) is for 86 revolutions per minute Z). From Table 2, the resin composition existing region is not given! For the sheet-like elastic foam substrate, even if the hardness of the material is increased with a high density or the like, Under the evaluation conditions, scratch resistance of 30 rotations or more could not be realized. In the density range in which 250 kg / m ³ or less and comprising 240 kg / m ³ of the test piece S (Measurement Example 2 and 5) of the present invention, a 20 or more rotations scratch resistance was confirmed to obtain ChikaraTsuta.

[0049] On the other hand, in the materials of measurement examples 1 to 4, no problem occurred in the use as a sealing member of a mobile phone or the like, and in the material of measurement example 5, the physical relationship with the member to be sealed Some damage was confirmed depending on the contact situation. In other words, in the current use as a seal member, it is necessary to develop scratch resistance capable of withstanding a rotation speed of 10 rotations or more, and preferably it is required to withstand a rotation speed of 30 rotations or more. It was confirmed that In Table 2, since all the results were “X” when the rotation speed was 43 or 86 rotations Z and the rotation speed was 50 rotations or more, 50 ~: LOO rotations are listed together.

[Table 2] a

. Speed: 43 rpm

• Rotation speed: 86 rpm

(Experiment 2) Integral retention by material (follow-up)

From the materials of Measurement Example 3 and Measurement Example 6 described in Experiment 1, eight sheet-like elastic foamed substrates of Measurement Example A "and Measurement Example C were prepared, respectively. A measurement example in which a 4 μm thick resin composition existing region was formed using a resin composition having various material properties (a to; j: 10 types) and having various material strengths A ′ ′-a to j And measurement examples C-a to j were produced for each sheet-like elastic body (20 sheets in total), and each of the produced sheet-like elastic bodies was subjected to the test described below to be integrated. The retention property (followability) was confirmed and evaluated.The method for producing the sheet-like elastic body was in accordance with the above-described example.

[Table 3]

• In Table 3, the elongation and tensile strength conform to JIS K 6251.

It is a measured value.

In Table 3, the abbreviations are as follows.

P U: Polyurethane, S B R: Styrene-butadiene rubber

P A: Polyamide, A C: Acrylic resin

T m: Melting temperature, T g: Glass transition temperature

[0051] (Evaluation of integral retention (followability))

Using a Φ10 round bar, press the sheet-like elastic body from the side where the resin composition is present so that it is recessed 0.5 mm at 50% compression, and visually check for the occurrence of wrinkles during this pressing. did. The results of visual inspection are as follows: ◎: no generation of the sheet, ○: generation of a sheet of less than 5 mm, A: generation of a sheet of 5 to 10 mm, X: generation of a sheet of 10 mm or more. evaluated. In this evaluation, when the integral retention of the resin composition existing region is high, the resin composition existing region is closely deformed with respect to the deformation of the sheet-like elastic foamed substrate, and the external shape is changed. If the strain is not obvious and low, the region where the resin composition is present cannot cope with the deformation of the sheet-like elastic foamed substrate, and an evaluation method using the fact that geometric distortion appears outside. is there.

[0052] (Result of Experiment 2)

Table 4 (a) below shows the results of measurement example A ′ ′ system, and Table 4 (b) shows the results of measurement example C system. From Table 4, it was confirmed that the resin composition existing region consisting of a raw material material having low elongation has poor integral retention (followability).

[Table 4] Material material

V-shaped mm followability V-shaped followability inertial substrate composition << »characteristics * body

Measurement example A "-a A" a ◎ Measurement example (: -a 〇 a ® Measurement example A "-b † b ◎ Measurement example [-b † b ◎ Measurement example A" -c † c ® Measurement example Cc Individual c

Measurement example A "-d individual d ◎ measurement example [-dd ◎ measurement example A" -e † e © Measurement example [-e individual e ◎ measurement example A "-f † f X measurement example [-ff X measurement example A "-q T q X. Measurement example [-q pcs q X Measurement example A" -hh ◎ Measurement example [-hh ® Measurement example A "-ii ◎ Measurement example [-i † i ◎ Measurement example A"-j T i ◎ Measurement example [-ji ◎

(Experiment 3) Scratch resistance and integral retention (trackability) depending on the thickness of the region where the resin composition exists

Twenty A "-based sheet-like elastic foam substrates were fabricated from the material of Measurement Example 3 according to Experiment 1, and twenty C-based sheet-like elastic foam substrates were fabricated from the material of Measurement Example 6. In addition, using the materials with the physical properties (a to; j: 10 types) shown in Table 5 (A "series") and Table 6 (C series) below, Example of an ats to which a region where the fat composition is present was given A "—1 to 16 and Comparative Example A” —1 to 4, and Example C—1 to 16 and Comparative Example C—1 to 4 One body was prepared (40 in total). For the sheet-like elastic bodies according to each of the examples and comparative examples, the scratch resistance (rotation rate of 43 rotations for Z rotation (some rotations of 86 rotations were also performed)) performed in Experiment 1 was obtained. We confirmed and evaluated the integral retention (follow-up performance) performed in Experiment 2. The manufacturing method of the sheet-like elastic body was the same as that of the above-mentioned example as in Experiment 2.

[Table 5]

[Table 6]

(Result of Experiment 3)

The results are shown in Table 5 and Table 6 above. From Table 5 and Table 6, it is possible to achieve 10 rotations or more under the evaluation conditions by setting the thickness of the resin composition existing region to 1 μm or more in any material sheet-like elastic foam substrate. It was confirmed that good follow-up performance was exhibited by setting it to m or less. In addition, by setting the thickness of the resin composition existing area to 2 m or more, the scratch resistance level suitable for 30 rotations can be exceeded, exceeding the scratch resistance level of the seal members that are currently favorably used. confirmed. Furthermore, by setting the thickness of the resin composition existing region to 3 m or more, scratch resistance was confirmed even for 100 revolutions. In addition, for 3 m, scratch resistance was confirmed even under the condition of 86 revolutions Z (the mark in the upper right corner of the scratch resistance result column indicates that even under the condition of revolutions 86 revolutions Z). Similarly, it was “〇”). Regarding the followability, “性” was confirmed at 10 / zm or less, and it was confirmed that the sheet-like elastic foamed substrate and the resin composition existing region were bonded with very high adhesion. In Comparative Examples A "—2 and 3, and Comparative Examples C—2 and 3, the thickness of the resin composition existing area is 3 m, but the elongation of the material forming the resin composition existing area is In the problem, it was confirmed that there was a problem in the integral retention (followability).

The thickness of the resin composition existing area was fixed to 3 μm, and three sheet-like elastic foam substrates were used from the material of Measurement Example 1 in Experiment 1, and the material force of Measurement Example 2 was used as the sheet-like elastic foam substrate. 3 sheets, material strength of measurement example 4 each 3 sheet-like elastic foam substrate, from measurement example 5 material 3 sheet-like elastic foam substrate and measurement example 7 material force 1 sheet-like elastic foam substrate Produced. Then, as shown in Table 7 below, a sheet-like elastic body provided with a resin composition existing region using each material having each physical property (ac: 3 types (measurement example 7 is only a)) is provided. Each one was prepared (13 sheets in total). Each sheet-like elastic body produced was observed and evaluated for scratch resistance (rotation speed 43 and 86 rotations Z) and followability. As a result, in the sheet-like elastic bodies according to Measurement Example 5 and Measurement Example 7, problems other than the scratch resistance exceeding the limit when the rotation speed exceeded 100 could not be confirmed.

[Table 7] Material Scratch resistance (rotation speed)

Mm M Tracking performance 43 rev / min 86 rev / min

β 10 ~ 90 100 10 ~ 90 100

A a 3.0 ◎ O ○ ○ ○

† b † ◎ 〇 O 〇〇

† c ○ O ○ ○

A 'a ® 〇 O O O

† c ® O ○ ○ O

Α '"a † ◎ 〇 O 〇 O

Individual b ® ○ O O ○

t c † ◎ ○ ○ ○ ○

B a ® O Δ O Δ

Individual b † ◎ ○ Δ ○ Δ

† c † ◎ ○ ○ ○ O

D a 1 ◎ ○ O ○ Δ

Claims

The scope of the claims

[1] In a sheet-like elastic body comprising a sheet-like elastic foam substrate (12),

The entire one surface (12a) in the thickness direction of the sheet-like elastic foam substrate (12) is covered with the resin composition (R),

In the surface layer portion of the surface (12a), the resin composition (R) is present in the cell (28) defined by the foam skeleton (13) constituting the sheet-like elastic foam substrate (12). ,

As a result, a resin composition existing region (14) in which the sheet-like elastic foam substrate (12) and the resin composition (R) are integrated is formed in the surface layer portion.

A sheet-like elastic body.

[2] The sheet-like composition according to claim 1, wherein the resin composition-existing region (14) is formed by fusing the resin composition (R) and the foam skeleton (13) together at a contact site. Elastic body.

[3] The resin composition existing area (14) is, based on JIS K 7218, (1) Stainless steel, (2) Load 1.2kg, (3) Rotation speed The sheet-like elastic body according to claim 1 or 2, which has a resistance of 10 rotations or more in an evaluation carried out under a condition of 43 rotations Z minutes.

[4] A sheet-like elastic body provided with a sheet-like elastic foam substrate (12),

The sheet-like elastic foam substrate (12) has a 50% compression load of 0.025 MPa or less and a 75% compression load of 0.40 MPa or less.

As a result, the sheet-like elastic foamed substrate (12) and the resin composition (R) are integrally formed on the surface layer portion of the surface (12a), and the material of the contact pressing body is determined based on JIS K 7218 ( (1) Stainless steel, (2) 1.2 kg load, (3) Resin composition existing area with resistance of 10 revolutions or more when evaluated under the condition of 43 revolutions and 43 minutes (14 ) Is formed. A sheet-like elastic body.

[5] The sheet-like elastic body according to any one of [1] to [4], wherein the thickness of the rosin composition existing region (14) ranges from 1 to 25 μm.

[6] The tensile strength according to JIS K 6251 of the resin composition (R) is in the range of 1.0 to 80 MPa. The sheet-like elastic body according to any one of claims 1 to 5.

The elongation defined in JIS K 6251 in the substance constituting the resin composition existing region (14) is greater than or equal to the elongation defined in JIS K 6251 of the sheet-like elastic foam substrate (12). The sheet-like elastic body according to any one of -6.