JPH10245494A - Elastic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily prevent the bleeding of a plasticizer from an elastomer compounded with the plasticizer, and obtain an elastic material keeping comfortable feeling to the skin and useful e.g. as a seat for vehicle by making the material include a fluorine-based surfactant. SOLUTION: This elastic material is composed of (A) a plasticizer, (B) an elastomer compounded with the component A and (C) a fluorine-based surfactant compounded to the component B to prevent the migration of the component A to the surface of the component B. Preferably, the amount of the component C in the component B is 0.01-5wt.%, the component A is a phosphoric acid ester compound (e.g. tricresyl phosphate) and the component B is an elastomer composed mainly of a polyurethane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an elastic body useful as a cushioning material for furniture, bedding, etc., and more particularly to a cushioning material for a vehicle seat or a cushioning material for a steering wheel, a handle grip, etc. in an automobile or a motorcycle. Is
The present invention relates to an elastic body capable of suppressing bleeding (migration) of a plasticizer as much as possible and maintaining a comfortable feeling of use on the skin for a long time.

[0002]

2. Description of the Related Art As an elastic body utilizing the elasticity of a polymer material, for example, natural rubber, diene rubber such as chloroprene, isoprene, butadiene, butyl rubber, ethylene-propylene rubber, urethane rubber, silicone rubber,
Acrylic rubbers, rubbers such as non-diene rubbers such as fluoro rubbers, and thermoplastic elastomers utilizing block copolymers and polymer alloys of these rubbers and thermoplastic polymers, among which urethane-based Are used in a wide range of fields because of their excellent mechanical properties.

When the above elastic body is used as a shock absorbing material, if elasticity and flexibility are emphasized, strength and solvent resistance are inferior, and conversely, high Tg (glass transition temperature) is required to increase strength and solvent resistance. It is well known that a dense polymer structure reduces elasticity and flexibility. It is difficult only to adjust the polymer composition and the crosslink density to achieve such contradictory properties. Therefore, a plasticizer is often added. However, many of the widely used plasticizers are low molecular weight compounds such as phthalic acid esters and phosphoric acid esters. The problem of bleeding (shifting) occurs. In particular, if the elastic product touches human skin, for example, the bleeding plasticizer gives a sticky and unpleasant touch. In addition, the bleed reduces the substantial amount of the plasticizer present inside the elastic body, and thus has the disadvantage of deteriorating the characteristics of the product.

For this reason, various studies have been made on a high molecular weight plasticizer of a polyester type in which the molecular weight of the plasticizer is increased, a polymer alloy, internal plasticization, and the like.
At present, there is no plasticizing means with good plasticizing efficiency. In addition, they found the optimal plasticizer and compounding amount that can balance the polymer composition and properties, but because of the bleeding problem, the type and amount of plasticizer according to the polymer composition were studied from scratch. This is a waste of cost and time, and from such a viewpoint, a method for easily preventing bleeding of the plasticizer has been demanded.

[0005]

SUMMARY OF THE INVENTION Therefore, in the present invention, a method for easily preventing bleeding of a plasticizer in an elastic body containing a plasticizer has been found. Providing is an issue.

[0006]

The present invention relates to an elastic body containing a plasticizer, wherein the elastic body contains a fluorine-based surfactant for preventing the plasticizer from migrating to the surface of the elastic body. It has the greatest features where it is located (claim 1). By blending this fluorine-based surfactant, bleeding of the plasticizer could be suppressed as much as possible, and stickiness of the surface of the elastic body could be prevented.

[0007] In order to prevent the plasticizer from migrating to the surface of the elastic body, the content of the fluorine-based surfactant must be 0.0% in the elastic body.
It is preferably contained in an amount of 1 to 5% by weight (claim 2). Although the present invention does not limit the types of the elastic body and the plasticizer, the elastic body has a polyurethane as a main component, and exhibits a further effect when the plasticizer is a phosphate compound. (Claim 3).

Further, a layer made of a fluorine-based surfactant for preventing the plasticizer from migrating to the surface of the elastic body is formed on a part or the entire surface of the elastic body containing the plasticizer. The body is also included in the present invention, and in the case of the present invention,
The transfer of the plasticizer can be easily prevented (claim 4). The raw material of the elastic body may include a fluorine-based surfactant, and a layer made of the fluorine-based surfactant may be formed on part or all of the surface of the elastic body (claim 5).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The elastic body of the present invention has a point in that bleeding of a plasticizer is suppressed by using a plasticizer and a fluorine-based surfactant in combination. The fluorine-based surfactant may be present inside the elastic body or on the surface of the elastic body, and both are effective in suppressing bleeding of the plasticizer. In addition, the elastic body designed with a polymer so that it is relatively soft, not only because of the bleeding of the plasticizer, but also has a slightly sticky surface when the elastic body is left in a high temperature environment for a long time, Although it may be sticky, it has been found that such an effect of preventing tackiness is also exhibited by the use of a fluorine-based surfactant.

As the material of the elastic body, natural rubber, diene rubber such as chloroprene, isoprene, butadiene, butyl rubber, ethylene-propylene rubber, urethane rubber,
Rubbers such as non-diene rubbers such as silicone rubber, acrylic rubber and fluorine rubber; SBS (styrene-butadiene-
(Styrene), SIS (styrene-isoprene-styrene), SEBS (styrene-ethylene-butadiene-styrene), SEPS (styrene-ethylene-propylene-styrene), and other polystyrene-based thermoplastic elastomers; polyolefin-based, polyester-based, and polyamide-based elastomers Known thermoplastic elastomers such as polyurethane, fluoropolymer and the like can be used. Among them, urethane rubber containing polyurethane as a main component or polyurethane thermoplastic elastomer is particularly preferably used in the application of the present invention.

Polyol components that can be used in the production of polyurethane include ethylene glycol, propylene glycol, hydroquinone, bisphenol A,
1,6-hexanediol, glycerin, 1,2,6-
Low molecular weight polyols such as hexanetriol and pentaerythritol, polypropylene glycol (PPG),
An amine such as methylamine, n-butylamine, aniline, or melamine was added to the end of polyethylene glycol (PEG) -modified polypropylene glycol (adduct or PEG-PPG-PEG block, etc.), polytetramethylene glycol, or polyether polyol. Various modified polyether polyols such as polyether polyamine and urethane, polyether polyols such as polymer polyols, dibasic acids such as adipic acid and phthalic acid, ethylene glycol, 1,4-butanediol, and trimethylolpropane Polyester polyols such as polycondensed polyester polyols, polycaprolactone polyols, and polycarbonate polyols obtained by a condensation reaction with polyols such as acrylic polyols and polybutadienes Polyols, ethylene - partially saponified products of vinyl acetate copolymer (EVA). These polyols can be combined with ones having different molecular weights, different numbers of functional groups and the like as appropriate to produce elastic bodies having desired properties. Among them, preferred are PPG, modified PP
G, PEG-PPG-PEG block and the like.

The isocyanate component includes tolylene diisocyanate (TDI), crude tolylene diisocyanate (crude TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), polymethylene polyphenyl isocyanate (polymeric MDI, Or Crude M
DI), hexamethylene diisocyanate (HDI),
Trizine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), norbornene diisocyanate (NBD)
I) and urethane prepolymers. Commonly used are TDI, MDI, polymeric MDI, IPD
I is not particularly limited.

At the time of polyurethane production, it is preferable to use an organic metal or amine compound such as dibutyltin dilaurate or stannas octoate as a catalyst. When the elastic body is used as a shock absorbing material, it may be foamed by a known method.

The plasticizer is not particularly restricted but includes triphenyl phosphate (TPP), tricresyl phosphate (TCP), and trixylylenyl phosphate (TX).
P), cresyl diphenyl phosphate (CDP), tris (chloroethyl) phosphate (TCEP), tris (dichloropropyl) phosphate, and other phosphoric ester compounds, and di-2-ethylhexyl phthalate (D
Phthalic acid ester compounds such as OP) and aliphatic dibasic acid esters such as di-2-ethylhexyl sebacate (DOS) and di-2-ethylhexyl adipate (DOA). In particular, in order to impart flame retardancy to the elastic body, it is preferable to use a phosphate ester-based plasticizer such as TPP or TCP in an amount of 5% by weight or more based on all the raw materials of the elastic body. It is recommended that the use amount of these plasticizers is appropriately changed depending on the material, use, and the like of the elastic body, but usually, it is preferably 75% by weight or less, more preferably 50% by weight or less based on all raw materials of the elastic body. . If the amount of the plasticizer exceeds 75% by weight, bleeding of the plasticizer cannot be prevented even by applying the present invention.

On the other hand, the most important components in the present invention, fluorine surfactants include fluorinated alkyl ester compounds, perfluoroalkyl carboxylate salts, perfluoroalkyl group-containing oligomers, and perfluoroalkyl ethylene oxide addition. Products, perfluoroalkyl alkoxylates, perfluoroalkyl phosphates, perfluoroalkyl sulfonic acid esters, perfluoroalkyltrimethylammonium salts, and the like. When the fluorine-based surfactant is added to the raw material of the elastic body, 0.01 to
It is preferable to use it in the range of 5% by weight. If the amount is less than 0.01% by weight, the effect of preventing the bleeding of the plasticizer is insufficient, and if the amount exceeds 5% by weight, the effect is saturated, and it is useless.

On the other hand, the above-mentioned fluorine-based surfactant can also be obtained by providing the layer on the surface of an elastic body having a desired form.
Bleeding of the plasticizer can be prevented. About the method of forming a layer of a fluorine-based surfactant on the elastic body surface,
There is no particular limitation, and it may be applied by a brush coating method, a spray coating method, a roll coating method, a dip coating method, a bar coating method, or the like in a solution state in which the fluorine-based surfactant is used as it is or in a mixed state with water or a hydrophilic solvent. The fluorine-based surfactant layer is preferably formed on the entire surface of the elastic body, but this layer is partially formed as long as the bleeding of the plasticizer can be prevented by the presence of the fluorine-based surfactant layer. And may be partially discontinuous, as in the case of layers formed by spray coating.

If necessary, the elastic body may contain fine hollow particles which effectively act as a weight-reducing material or as a material for improving the impact absorbing ability. As such minute hollow particles, glass balloons (for example, “CEL-STAR”)
Z "series: manufactured by Asahi Glass Co., Ltd., Shirasu balloon (for example," Gallolite ": manufactured by Shiraishi Kogyo Co., Ltd.," Philite ": manufactured by UK, provided by Nippon Philite," Terra Balloon "and" Terafine ": manufactured by Calsheet), porous Calcium carbonate (for example, "Callite-KT" Shiroishi Central Research Institute) silica balloon, fly ash balloon, alumina, zirconia, pitch-based inorganic materials, phenol-based,
Polymer materials such as polyvinyl alcohol, polyvinylidene chloride, epoxy resin, and urea resin can be used. Above all, in order to ensure shock absorption, fine hollow particles that can be deformed by an external force are preferable, and from this point, the use of polymer material-based particles is recommended. In particular, a polyvinylidene chloride-based compound obtained by slightly copolymerizing acrylonitrile with vinylidene chloride is preferable because of its excellent deformability. Specifically, “Expancel DE” (made by Sweden Expancel, average particle size of 40 to 60 μm) in which the outer shell of polyvinylidene chloride is filled with butene gas.
And Microsphere series manufactured by Matsumoto Yushi Co., Ltd. These fine hollow particles are 1 to 1 in all raw materials of the elastic body.
It is preferable to use it in the range of 10% by weight. 1% by weight
If the amount is smaller, the effect of reducing the weight and improving the shock absorption is insufficient. The size of the fine hollow particles is not particularly limited, and those having a size of about several μm to several hundred μm can be used.

[0018]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention.
Modifications and alterations that do not depart from the spirit described below are all included in the technical scope of the present invention. In the following examples, “parts” means “parts by weight”. The characteristic evaluation methods used in the following examples and comparative examples are as follows.

[Contact Angle] Water and n-dodecane were dropped on an elastic sample, and the contact angle of the drop formed in contact with the sample surface was measured.

[Presence or absence of bleed] At room temperature (25 ° C.)
The elastic sample was allowed to stand for 0 hours, and the surface was visually observed for the presence or absence of bleeding of the plasticizer at that time.

[Shear Peeling Force] Elastic samples were stuck together and peeling force was measured when peeled at 90 °, and a relative value when the value of Comparative Example was set to 100 was shown.

Example 1 Molecular weight (Mw) of a polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer (hereinafter abbreviated as EPE) in which polyethylene glycol is bonded to both ends of a polypropylene glycol portion.
A polyol component was prepared by mixing 70 parts of 2,000 and 30 parts of 7000. As an isocyanate component, 25 parts of polymethylene polyphenyl isocyanate (polymeric MDI) was used. 30 parts of tricresyl phosphate were used as a plasticizer, and 3.5 parts of polyvinylidene chloride-based microballoons were used as a lightweight material. As the fluorine-based surfactant, 0.5 parts by weight of "Fluorad FC-430" (manufactured by 3M USA; nonionic; fluorinated alkyl ester; active ingredient 100%) was used. The above-mentioned elastic raw materials were thoroughly mixed, defoamed under reduced pressure, and then cast-molded to obtain an elastic molded product. The characteristics evaluation results are shown in Table 1.

Examples 2 to 4 In Example 2, "Surflon S383" (manufactured by Asahi Glass Co .; nonionic; perfluoroalkyl group-containing oligomer; 50% of active ingredient) was used as a fluorine-based surfactant.
In Example 3, 1.0 part of "MegaFac MCF300" (manufactured by Dainippon Ink and Chemicals, nonionic; active ingredient 30%) was used in Example 3, and in Example 4, "Megafac MCF310" was used.
An elastic body was obtained in the same manner as in Example 1 except that 1.0 part of (Dai Nippon Ink Chemical; nonionic; active ingredient 30%) was used. The characteristics evaluation results are shown in Table 1.

Comparative Example 1 An elastic material was obtained in the same manner as in Example 1 except that no fluorine-based surfactant was used. The characteristics evaluation results are shown in Table 1.

Example 5 The surface of the elastic material obtained in Comparative Example 1 was coated with a fluorosurfactant "Surflon S383" by a dip coating method. The characteristics evaluation results are shown in Table 1.

[0026]

[Table 1]

[0027]

The present invention has succeeded in preventing the migration of the plasticizer to the surface of the elastic body by using the fluorine-based surfactant together with the plasticizer. Therefore, the elastic recovery force, shock absorption, or flexibility of the elastic body does not change over time due to the decrease due to the migration of the plasticizer, and the elastic body surface may become sticky with the plasticizer, giving an unpleasant touch. Absent. Furthermore, since the effect of reducing the adhesiveness of the elastic body surface was also exhibited, inconvenience such as blocking does not occur, and the handleability is good.

The present invention can be applied to various elastic materials using a plasticizer by a very simple means of allowing the fluorine-based surfactant to be present inside the elastic material or only on the surface of the elastic material. There is no need to perform complicated studies such as changing the composition of the polymer or the composition of the plasticizer, and the method is practical.

The elastic body of the present invention can be used as a seat for automobiles, motorcycles and other vehicles, or as a cushioning material for handles, handle grips, etc., various materials such as automobile ceiling materials, door trim materials, pad materials and furniture. In addition to cushioning materials used for bedding and the like, cushioning materials for sports shoes and shoe soles, it can be applied to a wide range of fields as heat insulating materials, sound absorbing materials, cushioning materials and the like.

Claims (5)

[Claims] 1. An elastic body containing a plasticizer, wherein a fluorine-based surfactant for preventing the plasticizer from migrating to the surface of the elastic body is contained in the elastic body. Elastic body. 2. The method according to claim 1, wherein the fluorine-based surfactant contains 0.1% in the elastic body.
The elastic body according to claim 1, which is present in an amount of from 0.01 to 5% by weight. 3. The elastic body according to claim 1, wherein the elastic body is mainly composed of polyurethane, and the plasticizer is a phosphate compound. 4. An elastic body containing a plasticizer, wherein a layer made of a fluorine-based surfactant for preventing the plasticizer from migrating to the surface of the elastic body is provided on a part or the entire surface of the elastic body. An elastic body characterized by being formed. 5. The elastic body according to claim 4, wherein a fluorine-based surfactant is also contained inside the elastic body.