JPH05138747A - Sintered sheet and production thereof - Google Patents

Abstract

(57) [Summary] (Correction) [Purpose] To provide a sintered sheet 7 which is free from wrinkles and tears, has a texture excellent in surface appearance and softness, and is lightweight and clean. [Composition] A sintered sheet formed by molding a thermoplastic elastomer powder 5 having a specific viscoelasticity by a powder sintering method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sintered sheet used for automobile interior materials and electric products and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, skin materials used for automobile interior materials and electric products are manufactured in large quantities by calender rolls, extrusion molding and the like. Further, in recent years, high-grade skin materials having an improved aesthetic appearance and a soft feeling have been manufactured by a powder molding method using vinyl chloride resin powder. Further, a skin material having a foamed layer lined to provide cushioning properties is also manufactured.

[0003]

However, the skin material produced by calender rolls or extrusion molding has a disadvantage that the shearing force at the time of processing causes the texture pattern formed on the surface to be flowed or deformed in the post processing. Have. Also,
The skin material made of vinyl chloride resin has disadvantages such as a problem of recycling at the time of disposal and a problem of air pollution of acidic substances generated by incineration.

[0004]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a sintered sheet obtained by molding a thermoplastic elastomer powder having a specific viscoelasticity by a powder sintering method has a surface appearance and They have found that they are excellent in softness, and have completed the present invention.

That is, the present invention provides a sintered sheet formed from the following thermoplastic elastomer powder by a powder sintering method. (A) A thermoplastic elastomer powder comprising an elastomer composition of an ethylene / α-olefin copolymer rubber and a polyolefin resin, or a mixture of an ethylene / α-olefin copolymer rubber and a polyolefin resin as a crosslinking agent. A thermoplastic elastomer powder composed of a partially crosslinked elastomer composition which is dynamically crosslinked in the presence of a substance having a frequency of 1 at a dynamic viscoelasticity measurement at 250 ° C.
The complex dynamic viscosity η ^* (1) measured in radians / second is 1.
5 × 10 ⁵ poise or less and a frequency of 1 radian /
The Newtonian viscosity index n calculated by the following equation using the complex dynamic viscosity η ^* (1) in seconds and the complex dynamic viscosity η ^* (100) at a frequency of 100 radians / second is 0.67 or less. Thermoplastic elastomer powder. n = {log eta ^* (1) -log eta ^* (100)} / 2

Further, the present invention provides a method for producing a sintered sheet from powder by a powder sintering method, which comprises using the following thermoplastic elastomer powder (A) as the powder. To do. (A) A thermoplastic elastomer powder comprising an elastomer composition of an ethylene / α-olefin copolymer rubber and a polyolefin resin, or a mixture of an ethylene / α-olefin copolymer rubber and a polyolefin resin as a crosslinking agent. A thermoplastic elastomer powder composed of a partially crosslinked elastomer composition which is dynamically crosslinked in the presence of a substance having a frequency of 1 at a dynamic viscoelasticity measurement at 250 ° C.
The complex dynamic viscosity η ^* (1) measured in radians / second is 1.
5 × 10 ⁵ poise or less and a frequency of 1 radian /
The Newtonian viscosity index n calculated by the following equation using the complex dynamic viscosity η ^* (1) in seconds and the complex dynamic viscosity η ^* (100) at a frequency of 100 radians / second is 0.67 or less. Thermoplastic elastomer powder. ^{n = {logη * (1)} -logη * (100)} / 2

In the present invention, a non-foamed sheet layer formed by the powder sintering method from the thermoplastic elastomer powder of the following (A), and a pyrolytic foaming agent to the thermoplastic elastomer powder of the following (A), Another object of the present invention is to provide a multilayer sintered sheet comprising a foamed sheet layer formed by a powder sintering method from a foamable thermoplastic elastomer powder composition containing a pyrolytic foaming agent and a liquid coating agent. (A) A thermoplastic elastomer powder comprising an elastomer composition of an ethylene / α-olefin copolymer rubber and a polyolefin resin, or a mixture of an ethylene / α-olefin copolymer rubber and a polyolefin resin as a crosslinking agent. A thermoplastic elastomer powder composed of a partially crosslinked elastomer composition which is dynamically crosslinked in the presence of a substance having a frequency of 1 at a dynamic viscoelasticity measurement at 250 ° C.
The complex dynamic viscosity η ^* (1) measured in radians / second is 1.
5 × 10 ⁵ poise or less and a frequency of 1 radian /
The Newtonian viscosity index n calculated by the following equation using the complex dynamic viscosity η ^* (1) in seconds and the complex dynamic viscosity η ^* (100) at a frequency of 100 radians / second is 0.67 or less. Thermoplastic elastomer powder. ^{n = {logη * (1)} -logη * (100)} / 2

Further, the present invention is a non-foaming powder and a method for producing a multilayer sintered sheet from a foaming powder by a powder sintering method.
Of the thermoplastic elastomer powder of (A) below as a foamable powder, and a thermolytic foaming agent, or a thermolytic foaming agent and a liquid coating agent. The present invention provides a method for producing a multilayer sintered sheet, which is characterized by using a powder composition. (A) A thermoplastic elastomer powder comprising an elastomer composition of an ethylene / α-olefin copolymer rubber and a polyolefin resin, or a mixture of an ethylene / α-olefin copolymer rubber and a polyolefin resin as a crosslinking agent. A thermoplastic elastomer powder composed of a partially crosslinked elastomer composition which is dynamically crosslinked in the presence of a substance having a frequency of 1 at a dynamic viscoelasticity measurement at 250 ° C.
The complex dynamic viscosity η ^* (1) measured in radians / second is 1.
5 × 10 ⁵ poise or less and a frequency of 1 radian /
The Newtonian viscosity index n calculated by the following equation using the complex dynamic viscosity η ^* (1) in seconds and the complex dynamic viscosity η ^* (100) at a frequency of 100 radians / second is 0.67 or less. Thermoplastic elastomer powder. ^{n = {logη * (1)} -logη * (100)} / 2

The present invention will be described in detail below. The ethylene / α-olefin copolymer rubber used in the present invention,
A rubber containing olefin as a main component, for example, ethylene / propylene copolymer rubber, ethylene / propylene /
It is a non-conjugated diene copolymer rubber or the like. Examples of non-conjugated dienes include dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and the like. Among them, ethylene / propylene / ethylidene norbornene rubber (hereinafter EPDM)
Is used), an elastomer powder having excellent heat resistance and tensile properties can be obtained. In particular, ASTM D-9
The Mooney viscosity (ML _{1 + 4} 100 ° C.) measured at 100 ° C. according to 27-57T is 130 or more and 350 or less, preferably 200 or more and 300 or less per 100 parts by weight of ethylene / α-olefin copolymer rubber, An oil-extended olefin copolymer rubber containing 30 to 120 parts by weight of a mineral oil-based softening agent such as a paraffin-based process oil is preferable in terms of balancing tensile properties and fluidity.

As the polyolefin resin, polypropylene or a copolymer of propylene and α-olefin is preferably used. In particular, the hardness of the molded product can be reduced by using propylene and the α-olefin copolymer resin. 230 ° C according to JISK-7210,
Melt flow rate measured with a 2.16 kg load (MF
R) is preferably 20 g / 10 minutes or more, and particularly preferably 50 g / 10 minutes or more. The thermoplastic elastomer powder produced by using a polyolefin resin having a melt flow rate of less than 20 g / 10 minutes only softens the powder during powder molding, so that the powder particles are unlikely to melt and adhere to each other, and a strong molded product is obtained. I can't. The mixing ratio of the ethylene / α-olefin copolymer rubber and the olefin resin is from 5% to 80% by weight of the ethylene / α-olefin copolymer rubber and from 20% to 95% by weight of the olefin resin. Is preferred.

An organic peroxide is used as a cross-linking agent for dynamically cross-linking a mixture of an ethylene / α-olefin copolymer rubber and a polyolefin resin. Dialkyl peroxide is preferably used as the organic peroxide. Further, it is preferable to carry out dynamic crosslinking using an extremely small amount of organic peroxide in the presence of a crosslinking aid such as a bismaleimide compound. By doing so, ethylene / α-
The olefin copolymer rubber can be appropriately crosslinked to have heat resistance, and at the same time, high fluidity can be realized. At this time, the crosslinking aid is used in an amount of 1.5 parts by weight or less, preferably 0.6 parts by weight or less, based on 100 parts by weight of the mixture of the ethylene / α-olefin copolymer rubber and the polyolefin resin. Similarly, the organic peroxide as a crosslinking agent is used in an amount of 0.2 parts by weight or less, preferably 0.1 parts by weight or less, more preferably 0.07 parts by weight or less.

As a device used for dynamic crosslinking, a continuous kneading extruder such as a single-screw kneading extruder or a twin-screw kneading extruder is preferably used. Particularly, it is preferable to carry out continuous extrusion crosslinking at a shear rate of ≧ 10 ³ sec ⁻¹ using a twin-screw kneading extruder. When extrusion-crosslinking is performed at a shear rate of <10 ³ sec ^-1 , the dispersed particle size of the ethylene / α-olefin copolymer rubber becomes large and it becomes difficult to realize low viscosity.

The partially crosslinked elastomer composition produced under these conditions has a complex dynamic viscosity η ^* (1) of 1.5 × 10 ⁵ poise measured at a frequency of 1 radian / sec in a dynamic viscoelasticity measurement at 250 ° C. Below, preferably 1.0 × 10 ⁵
Below poise.

When the complex dynamic viscosity η ^* (1) measured at a frequency of 1 radian / second exceeds 1.5 × 10 ⁵ poise, the elastomer powder produced by using such an elastomer composition is melted on the mold surface. If this is not done, the powder cannot be molded by the powder sintering method, which has a very low shearing rate of 1 / sec ^-1 or less during processing.

The partially crosslinked elastomer composition produced under such conditions has a complex dynamic viscosity η measured at a frequency of 1 radian / sec in a dynamic viscoelasticity measurement at 250 ° C.
^* (1) and the complex dynamic viscosity η ^* (100) measured at a frequency of 100 radians / second, the Newtonian viscosity index n calculated by the following equation is 0.67 or less, preferably 0.60.
It is below. ^{n = {logη * (1)} -logη * (100)} / 2

When the Newtonian viscosity index n exceeds 0.67, even if the complex dynamic viscosity η ^* (1) measured at a frequency of 1 radian / second is 1.5 × 10 ⁵ poise or less, the complex dynamic viscosity The frequency dependence of the viscosity becomes large, and in the molding method such as the powder sintering method where the shaping pressure at the time of molding is as small as 1 kg / cm ² or less, thermal fusion between melted elastomer powder particles becomes incomplete. Only a molded product having low mechanical properties can be obtained.

As the elastomer used in the present invention, an uncrosslinked ethylene-α-olefin copolymer rubber or ethylene-α-olefin copolymer resin is used as the elastomer 10
By blending 50 parts by weight or less with respect to 0 parts by weight, an elastomer having excellent flexibility can be obtained. As the α-olefin in this case, propylene, butene and the like are used alone or in combination. In particular, the ethylene content is 40 to 90% by weight, preferably 70 to 85% by weight
Ethylene-propylene copolymer rubber of ML _{1+ 4} 100
A material having a temperature of 50 or less is preferable.

In the present invention, for the pulverization of the elastomer composition, a freeze pulverization method using liquid nitrogen is preferably used. −
The elastomer composition pellets cooled to 70 ° C. or lower, preferably −90 ° C. or lower can be obtained by a mechanical grinding method using a ball mill or the like. Grinding at a temperature higher than −70 ° C. is not preferable because the particle size of the crushed elastomer powder becomes coarse and the powder moldability decreases. In order to prevent the polymer temperature from becoming higher than the glass transition temperature during the pulverization operation, a method that generates less heat and has high pulverization efficiency is preferable. Further, it is preferable that the crushing device itself is cooled by external cooling.

The obtained elastomer powder is preferably pulverized to the extent that 95% or more of the total weight passes through the 32 mesh of Tyler standard sieve. If the cumulative rate on the 32 mesh screen exceeds 5%, this is one of the causes of uneven thickness during powder sintering. This unevenness in thickness gives unevenness to the flexibility of the molded product, and easily causes wrinkles, which becomes a factor that impairs the commercial value of the molded product.

As described above, the feature of the present invention is to provide an elastomer having a specific viscoelasticity which can be molded by the powder sintering method,
For example, pulverizing at a low temperature below the glass transition temperature to form a powder, and forming the powder into a sintered sheet (non-foaming sheet layer), or similar powder to which a thermal decomposition type foaming agent or a thermal decomposition type foaming agent is added. And a liquid coating agent to form a foamed sheet layer into a sintered sheet obtained by integrating the non-foamed sheet layer and the foamed sheet layer, and a method for producing the same.

The thermal decomposition type foaming agent used in the present invention is not particularly limited as long as it decomposes to generate a gas when heated and melted in powder sintering, and a general organic or inorganic chemical foaming agent is used. Can be used. Specifically, azo compounds such as azodicarbonamide, 2,2′-azobisisobutyronitrile, azohexahydrobenzonitrile, diazoaminobenzene, benzenesulfonylhydrazide, benzene-
1,3-sulfonyl hydrazide, diphenyl sulfone-
Sulfonyl hydrazide compounds such as 3,3′-disulfonyl hydrazide, diphenyl oxide-4,4′-disulfonyl hydrazide, 4,4′-oxybis (benzenesulfonyl hydrazide) and paratoluene sulfonyl hydrazide, N, N′-dinitroso Nitroso compounds such as pentamethylenetetramine, N, N'-dinitroso-N, N'-dimethylterephthalamide, terephthalazide, p
-Azide compounds such as tert-butylbenzazide and inorganic compounds such as sodium bicarbonate, ammonium bicarbonate and ammonium carbonate, and at least one of them is used. Among these, azodicarbonamide and 4,4 '
-Oxybis (benzenesulfonyl hydrazide) is preferred. The decomposition temperature of the thermal decomposition type foaming agent used in the present invention is usually 120 to 200 ° C, preferably 120 to 180 ° C.

Further, a foaming accelerator or a foaming aid may be used for the purpose of lowering the decomposition temperature of the thermal decomposition type foaming agent. Examples of the foaming accelerators or foaming aids are inorganic salts such as zinc white, zinc nitrate, lead phthalate, lead carbonate, trichlorophosphate, tribasic lead sulfate, zinc fatty acid soap, lead fatty acid soap, and cadmium. Examples thereof include metal soaps such as fatty acid soaps, borax, acids such as oxalic acid, succinic acid and adipic acid, urea, biurea, ethanolamine, glucose and glycerin.

On the other hand, a foaming inhibitor may be used for the purpose of raising the decomposition temperature of the thermal decomposition type foaming agent. Examples of foaming inhibitors include maleic acid, fumaric acid, phthalic acid, maleic anhydride, organic acids such as phthalic anhydride, stearoyl chloride, halogenated organic acids such as phthaloyl chloride,
Hydroquinone and other polyhydric alcohols, fatty acid amines, amides, oximes, isocyanates, and other nitrogen compounds, mercaptans, sulfides, and other sulfur compounds, phosphite and other phosphates, dibutyltin malate, tin chloride , Tin compounds such as tin sulfate, and hexachlorocyclopentadiene.

The thermal decomposition type foaming agent is usually 2 to 1 with respect to 100 parts by weight of the thermoplastic elastomer powder for powder sintering.
It is blended in an amount of 1 part by weight, preferably 3 to 7 parts by weight.

In the present invention, a liquid coating agent can be used at the same time as the above pyrolyzable foaming agent. The liquid coating agent used in the present invention is preferably a coating agent that cures at room temperature to 220 ° C. Specifically, thermosetting coating agents for protecting the surface of polysiloxane, melamine-based, urethane-based, fluorine-containing, etc. plastics, unsaturated polyesters, alkyds, oil-free alkyds, polyester resins such as linear polyester resins. , Amino resins such as melamine resin and modified melamine resin, novolac type,
Epoxy resin such as β-methyl epichloro type, cycloaliphatic type, acyclic aliphatic type, epoxidized fatty acid ester type, polycarboxylic acid ester type, aminoglycidyl type, chlorinated type, resorcin type, etc., oil modification, moisture curing block Polyurethane resin such as one-part type of epoxidized polyurethane resin, two-part type of catalyst-curing polyol-curing polyurethane resin, organic solvent type,
Examples of the acrylic resin include an acrylic acid ester such as an aqueous type and a solventless type, and a methacrylic acid ester as a main monomer. Among these liquid coating agents, polysiloxane, acyclic aliphatic type and cycloaliphatic type epoxy resin,
Solventless acrylic resins such as acrylic syrup are preferable, and among them, epoxy resins that cure at room temperature to 150 ° C. are particularly preferable.

The liquid coating agent is usually 50 at 25 ° C.
Those having a viscosity of about 50,000 cps can be used, but they can be diluted with a solvent before use. Further, in the present invention, an ordinary curing agent may be used in combination for the purpose of promoting the curing of the liquid coating agent.

As a curing agent for epoxy resin, for example,
Amine-based compounds such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 2,4,6-tris (dimethylaminomethyl) phenol, metaxylylenediamine, phthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, Examples thereof include acid anhydrides such as pyromellitic dianhydride, polyamide resins and mixtures thereof. Examples of the curing agent for the acrylic resin include organic materials such as dikrumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, benzoyl peroxide and laurocurperoxy. At least one peroxide can be used.

The liquid coating agent is generally added in an amount of 0.1 to 8 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the thermoplastic elastomer powder for powder molding. The curing agent used in combination with the liquid coating agent is usually added in an amount of 100 parts by weight or less based on 100 parts by weight of the liquid coating agent.

The manufacturing method of the present invention is a powder sintering method in which powder resin is directly heated to sinter, separate, and solidify. For example, the powder is evenly dispersed on a smooth belt and placed in a sintering furnace. It is a method of producing a sintered sheet by passing it through.

FIG. 1 is a schematic cross-sectional view showing an embodiment of the present invention. A thermoplastic elastomer powder 5 having a specific viscoelasticity is fed from a hopper 2 onto the endless belt 1 by a fixed amount. The thickness of the powder 5 is adjusted in the flow direction through the thickness adjusting plate 3.
The powder layer 4 is sintered in the sintering furnace 6 as the belt advances, and the sintered sheet 7 is manufactured. The surface temperature of the belt 1 is usually 100 to 300 ° C., and if the temperature is lower than 100 ° C., the sintered sheet 7 causes heat shrinkage when the powder is sintered, and pinholes are generated, which is not preferable.
If the temperature exceeds 300 ° C, the above powder causes thermal decomposition, which is not preferable. The temperature of the sintering furnace 6 is usually 160 to 30.
The temperature is 0 ° C, more preferably 180 to 280 ° C. The belt speed can be appropriately adjusted depending on the temperature of the sintering furnace and the state of the sintering sheet, but is usually 1 to 2 m / min. It is possible to give the belt a grain pattern, and when the belt is not grained, it is possible to give a grain pattern by an embossing roll. Further, release agent-treated paper and embossed paper can also be used.

When the foamed layer is molded, a thermoplastic elastomer powder having a specific viscoelasticity is mixed with a thermal decomposition type foaming agent, or a thermal decomposition type foaming agent and a liquid coating agent. A powder composition is used. For example, in the rear part of the endless belt 1 (on the right side in the drawing), the expandable thermoplastic elastomer powder composition 8 stored in the hopper 2 ′ is supplied onto the endless belt 1 as described above. The thermoplastic elastomer powder composition is supplied onto the sintered sheet (non-foamed sheet layer) 7 and the foamable thermoplastic elastomer powder composition layer 9 is formed through the thickness adjusting plate 3 ′. As the belt advances, it is sintered in a sintering furnace 6 ′ to produce a multilayer sintered sheet including a non-foamed sheet layer 7 and a foamed sheet layer 10. The temperature of the sintering furnace 6'is usually 160-30
The temperature is 0 ° C, more preferably 180 to 280 ° C.

Therefore, the thermoplastic elastomer powder and the expandable thermoplastic elastomer powder composition used in the powder sintering method are excellent in powder fluidity and are mainly used in the sintering furnace at a low shear rate and a low pressure. It must be easily melted by the heat supplied.

The heating method of the sintering furnace used in the powder sintering method according to the present invention is not particularly limited, and examples thereof include a gas heating furnace method, an electric heating furnace method, an infrared heating furnace method, and a heating medium. An oil circulation system, a high frequency induction heating system and the like can be mentioned, and these heating sources can also be used when foaming the melted powder composition.

The method of blending the thermal decomposition type foaming agent, or the thermal decomposition type foaming agent and the liquid coating agent, into the thermoplastic elastomer powder for powder sintering is not particularly limited. A method in which a pyrolytic foaming agent is previously mixed with the plastic elastomer powder and then a liquid coating agent is mixed with these compositions is preferable.

Further, when peeling a sheet powder-sintered with the thermoplastic elastomer powder or the expandable thermoplastic elastomer powder composition used in the present invention from the belt, the adhesion with the belt is strong, and if the peeling is forcibly attempted, the sheet will break. Wrinkles and bleaching problems may occur. For this reason,
In some cases, it may be necessary to coat the belt surface before molding by spraying a commonly used mold release agent such as dimethylpolysiloxane. In order to omit such an operation, it is effective to add a methylpolysiloxane compound as an internally added release agent to the elastomer powder composition in an amount of 2 parts by weight or less per 100 parts by weight of the elastomer powder composition. In this case, the timing of addition may be before or after pulverization. In this case, the methylpolysiloxane compound may have a viscosity at 25 ° C. of 20 centistokes or more. The preferred viscosity range is 50 to 5000 centistokes. If the viscosity becomes too high, the effect as a release agent decreases. Also,
If the amount of the internally added release agent exceeds 2 parts by weight, heat fusion between the elastomer powders is hindered, and only a sheet having poor mechanical properties can be obtained. Moreover, the internally added release agent bleeds onto the belt surface, and the belt is contaminated, which is not preferable.

In the present invention, known heat-resistant stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine- or amide-based stabilizers,
An antiaging agent, a weather resistance stabilizer, an antistatic agent, a lubricant such as metallic soap and wax, a pigment for coloring and the like can be added in a necessary amount.

The sintered sheet or the like of the present invention is applied to the surface of the sheet as a coating agent with a resin having excellent abrasion resistance such as polyurethane resin, acrylic resin or engineering plastic in order to improve scratch resistance or slipperiness. You can also do it. Further, such a coating agent can be applied to the surface of the product after molding.

[0038]

As described above in detail, according to the present invention,
The sintered sheet and the multilayer sintered sheet obtained by the powder sintering method are effective as a skin material because they have no wrinkles or tears and have a texture excellent in surface appearance and softness.

Further, the present invention can provide a sintered sheet and a multilayer sintered sheet which are lightweight and have excellent cleanliness. The sintered sheet or the like of the present invention is, for example, in the automobile field, an instrument panel, a console box, an armrest, a headrest, a door trim, a rear panel, a pillar trim,
Sun visor, luggage compartment trim, luggage compartment trim, airbag storage box, seat buckle,
Headliners, glove boxes, steering wheel covers, interior skin materials such as ceiling materials, kicking plates, change lever boots, interior moldings such as ceiling materials, spoilers, side moldings, license plate housings, mirror housings, air dam skirts, mudguards, etc. Suitable for automotive exterior parts.

Furthermore, the sintered sheet or the like of the present invention can be used for household appliances.
In the field of office automation equipment, for example, televisions, videos, washing machines, dryers, vacuum cleaners, coolers, air conditioners, pots,
Suitable for skins and housings such as jars, dishwashers, beauty appliances, CD / cassette storage boxes, personal computers, telephones, copiers, facsimiles, telex, etc.

In the field of sports products, the sintered sheet or the like of the present invention can be used as, for example, decorative parts for sports shoes, rackets for various ball games, grips for sports equipment and products, saddle skins and handle grips for bicycles, motorcycles and tricycles. Suitable.

The sintered sheet or the like of the present invention is used in the field of construction and housing, for example, as a skin material for furniture, desks, chairs, gates, etc.
Doors, fences and other skin materials, wall decoration materials, ceiling decoration materials, curtain wall skin materials, kitchen, washrooms, indoor floor materials such as toilets, balconies, terraces, balconies, carports and other outdoor floor materials, entrances Mat, tablecloth, coaster,
Suitable for rugs such as ashtray.

In addition to the above, the sintered sheet of the present invention,
For example, it is suitable for skin materials such as bags, cases, stationery, dolls, other toys, miscellaneous goods, and industrial parts.

[0044]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The decomposition temperature of the thermal decomposition type foaming agent was measured as follows. The sample was put in a capillary tube, heated at 2 ° C./min with a melting point measuring device (MP type manufactured by Yanagimoto Seisakusho), and the temperature at which the sample started foaming was measured as the decomposition temperature.

Example 1 Per 100 parts by weight of EPDM (ML _{1 + 4} 100 ° C. = 242, propylene content = 28% by weight, iodine value = 12) mineral oil-based softening agent (registered trademark Diana Process PW-380 manufactured by Idemitsu Kosan Co., Ltd.) ) Oil-extended EPDM with 100 parts by weight added
(ML _{1 + 4} 100 ° C. = 53) 40 parts by weight, propylene-ethylene random copolymer resin (ethylene content = 5% by weight, MFR = 85 g / 10 minutes) 60 parts by weight, and a crosslinking aid (Sumitomo Chemical, 0.4 parts by weight of Sumifine BM-Bismaleimide compound (registered trademark) is kneaded with a Banbury mixer for 10 minutes, and then pelletized into a master batch for crosslinking (hereinafter referred to as MB) using an extruder. did.

This M. B. 100 parts by weight of organic peroxide (manufactured by Sanken Kako, registered trademark Sampelox APO,
Add 0.04 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxynohexane), and use a twin-screw kneader (manufactured by Japan Steel Works, registered trademark TEX-44) at 220 ° C.
Was dynamically crosslinked to obtain an elastomer composition pellet. The pellets were cooled to a temperature of −100 ° C. using liquid nitrogen, and then freeze-pulverized to obtain a complex dynamic viscosity η ^* (1) of 3.1 × 10 ³ poise and a Newtonian viscosity index n of 0.2.
A thermoplastic elastomer powder for powder sintering of No. 4 was obtained. This powder passed through a 32 mesh Tyler standard sieve at 99% by weight.

As shown in FIG. 1, the thermoplastic elastomer powder 5 for powder sintering was put into the hopper 2 and the belt speed was adjusted to 1.75 m / min. The belt 1 was made of stainless steel and had a width of 30 cm and a thickness of 1 mm. The front sintering furnace 6 was set at 200 ° C. Rear sintering furnace 6 '
Did not use. The surface temperature of the belt was 120 ° C. The thickness adjusting plate 3 was adjusted to form a 2 mm powder layer 4. The powder layer 4 was introduced into the sintering furnace 6 as the belt progressed and was sintered. The obtained sintered sheet had a thickness of 0.7 mm, and its surface was uniformly smooth.

Example 2 The same thermoplastic elastomer powder 5 for powder sintering as in Example 1 was put into the hopper 2. Further, a foam formed by blending 100 parts by weight of the same thermoplastic elastomer powder for powder sintering with 5 parts by weight of a pyrolytic foaming agent azodicarbonamide (manufactured by Sankyo Kasei, Celmic CAP-500, decomposition temperature 150 ° C.) Thermoplastic elastomer powder composition 8 was put into hopper 2 '. On the sintered sheet (non-foamed sheet layer) manufactured in the same manner as in Example 1, the expandable thermoplastic elastomer powder composition 8 was placed in the hopper 2 '.
Then, the foamable powder composition layer 9 was formed by adjusting the thickness adjusting plate 3 '. The layer consisting of the non-foamed sheet layer and the expandable powder composition layer was passed through the rear sintering furnace 6'set at 200 ° C. The obtained sintered sheet was a multilayer sintered sheet in which a non-foamed sheet layer and a foamed sheet layer were integrated. In this multilayer sintered sheet, the non-foamed sheet layer had a thickness of 0.7 mm and the foamed sheet layer had a thickness of 2.5 mm. The surface of this multilayer sintered sheet was uniformly smooth and had good cushioning properties.

Example 3 The same thermoplastic elastomer powder 5 for powder sintering as in Example 2 was put into the hopper 2. Also the powder 100
Pyrolysis-type blowing agent azodicarbonamide (Sankyo Kasei, Celmic CAP-500, decomposition temperature 1 relative to parts by weight)
50 ° C.) 5 parts by weight, liquid coating agent (manufactured by Sumitomo Chemical,
The expandable thermoplastic elastomer powder composition 8 containing 0.5 parts by weight of registered trademark Sumiepoxy ELA115) and 0.05 parts by weight of triethylenetetramine was put into the hopper 2 '. Hereinafter, a multilayer sintered sheet in which the non-foamed sheet layer and the foamed sheet layer were integrated was manufactured under the same conditions as in Example 2. In this multilayer sintered sheet, the non-foamed sheet layer had a thickness of 0.7 mm and the foamed sheet layer had a thickness of 2.6 mm. The surface of this multilayer sintered sheet was uniformly smooth and had good cushioning properties.

Example 4 50 parts by weight of propylene-ethylene random copolymer resin (ethylene content = 3% by weight, MFR = 60 g / 10 minutes) was used, and 40 parts by weight of the oil-extended EPDM in Example 1 was added to 50 parts by weight. A thermoplastic elastomer powder for powder sintering having a complex dynamic viscosity η ^* (1) of 3.4 × 10 ⁴ poise and a Newtonian viscosity index n of 0.59 under the same conditions as in Example 1 except that Obtained. This powder passed through a 32 mesh Tyler standard sieve at 99% by weight. Example 2 against 100 parts by weight of powder similar to this powder
5 parts by weight of the same pyrolytic foaming agent was blended to obtain a foamable thermoplastic elastomer powder composition. Sintered sheet under the same conditions as in Example 2 except that a release paper with a grain (EV130TA-7, manufactured by Heiwa Paper Industry Co., Ltd.) was uniformly stuck on the belt, and the sintering furnace 6 in the front part was set to 230 ° C. Was manufactured.
The obtained sintered sheet was a multilayer sintered sheet in which a non-foamed sheet layer and a foamed sheet layer were integrated. In this multilayer sintered sheet, the non-foamed sheet layer had a thickness of 0.7 mm and the foamed sheet layer had a thickness of 2.5 mm. Further, this multilayer sintered sheet had a good appearance in which a grain pattern was transferred, and had excellent cushioning properties.

Comparative Example 1 50 parts by weight of a propylene-ethylene random copolymer resin (ethylene content = 3% by weight, MFR = 10 g / 10 minutes) was used, and 40 parts by weight of the oil-extended EPDM in Example 1 was added to 50 parts by weight. A thermoplastic elastomer powder having a complex dynamic viscosity η ^* (1) of 2.3 × 10 ⁵ poise and a Newtonian viscosity index n of 0.76 was obtained under the same conditions as in Example 1, except that This powder is 32 of Tyler standard sieve
98% by weight passed through a mesh sieve. Hereinafter, a sintered sheet was produced under the same conditions as in Example 1, but the powder had poor meltability, and the sintered sheet was not a uniform sheet due to frequent occurrence of pinholes.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a manufacturing process of a sintered sheet.

[Explanation of symbols]

 1 ... Belt 2 ... Hopper 2 '... Hopper 3 ... Thickness adjusting plate 3' ... Thickness adjusting plate 4 ... Thermoplastic elastomer powder layer 5 ... Thermoplastic elastomer powder 6 ... Sintering furnace 6 '... Sintering furnace 7 ... Sintered sheet (non-foamed sheet layer) 8 ... Expandable thermoplastic elastomer powder 9 ... Expandable thermoplastic elastomer powder layer 10 ... Expanded sheet layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadashi Hikasa 1-5 Anesaki Kaigan, Ichihara, Chiba Sumitomo Chemical Co., Ltd. Within the corporation

Claims (4)

[Claims] 1. A sintered sheet formed from the following thermoplastic elastomer powder (A) by a powder sintering method. (A) A thermoplastic elastomer powder comprising an elastomer composition of an ethylene / α-olefin copolymer rubber and a polyolefin resin, or a mixture of an ethylene / α-olefin copolymer rubber and a polyolefin resin as a crosslinking agent. A thermoplastic elastomer powder composed of a partially crosslinked elastomer composition which is dynamically crosslinked in the presence of a substance having a frequency of 1 at a dynamic viscoelasticity measurement at 250 ° C.
The complex dynamic viscosity η ^* (1) measured in radians / second is 1.
5 × 10 ⁵ poise or less and a frequency of 1 radian /
The Newtonian viscosity index n calculated by the following equation using the complex dynamic viscosity η ^* (1) in seconds and the complex dynamic viscosity η ^* (100) at a frequency of 100 radians / second is 0.67 or less. Thermoplastic elastomer powder. ^{n = {logη * (1)} -logη * (100)} / 2 2. A method for producing a sintered sheet from powder by a powder sintering method, wherein the following thermoplastic elastomer powder (A) is used as the powder. (A) A thermoplastic elastomer powder comprising an elastomer composition of an ethylene / α-olefin copolymer rubber and a polyolefin resin, or a mixture of an ethylene / α-olefin copolymer rubber and a polyolefin resin as a crosslinking agent. A thermoplastic elastomer powder composed of a partially crosslinked elastomer composition which is dynamically crosslinked in the presence of a substance having a frequency of 1 at a dynamic viscoelasticity measurement at 250 ° C.
The complex dynamic viscosity η ^* (1) measured in radians / second is 1.
5 × 10 ⁵ poise or less and a frequency of 1 radian /
The Newtonian viscosity index n calculated by the following equation using the complex dynamic viscosity η ^* (1) in seconds and the complex dynamic viscosity η ^* (100) at a frequency of 100 radians / second is 0.67 or less. Thermoplastic elastomer powder. ^{n = {logη * (1)} -logη * (100)} / 2 3. A non-foamed sheet layer formed from a thermoplastic elastomer powder of the following (A) by a powder sintering method, and a thermal decomposition type foaming agent to the thermoplastic elastomer powder of the following (A), or thermal decomposition. A multilayer sintered sheet comprising a foamed sheet layer formed by a powder sintering method from a foamable thermoplastic elastomer powder composition containing a mold foaming agent and a liquid coating agent. (A) A thermoplastic elastomer powder comprising an elastomer composition of an ethylene / α-olefin copolymer rubber and a polyolefin resin, or a mixture of an ethylene / α-olefin copolymer rubber and a polyolefin resin as a crosslinking agent. A thermoplastic elastomer powder composed of a partially crosslinked elastomer composition which is dynamically crosslinked in the presence of a substance having a frequency of 1 at a dynamic viscoelasticity measurement at 250 ° C.
The complex dynamic viscosity η ^* (1) measured in radians / second is 1.
5 × 10 ⁵ poise or less and a frequency of 1 radian /
The Newtonian viscosity index n calculated by the following equation using the complex dynamic viscosity η ^* (1) in seconds and the complex dynamic viscosity η ^* (100) at a frequency of 100 radians / second is 0.67 or less. Thermoplastic elastomer powder. ^{n = {logη * (1)} -logη * (100)} / 2 4. A non-expandable powder and a method for producing a multilayer sintered sheet from the expandable powder by a powder sintering method, wherein the thermoplastic elastomer powder (A) below is used as the non-expandable powder and the expandable powder is used. Multilayer firing characterized by using a foamable thermoplastic elastomer powder composition obtained by blending a thermoplastic decomposition powder of the following (A) with a thermal decomposition foaming agent or a thermal decomposition foaming agent and a liquid coating agent. A method for manufacturing a binding sheet. (A) A thermoplastic elastomer powder comprising an elastomer composition of an ethylene / α-olefin copolymer rubber and a polyolefin resin, or a mixture of an ethylene / α-olefin copolymer rubber and a polyolefin resin as a crosslinking agent. A thermoplastic elastomer powder composed of a partially crosslinked elastomer composition which is dynamically crosslinked in the presence of a substance having a frequency of 1 at a dynamic viscoelasticity measurement at 250 ° C.
The complex dynamic viscosity η ^* (1) measured in radians / second is 1.
5 × 10 ⁵ poise or less and a frequency of 1 radian /
The Newtonian viscosity index n calculated by the following equation using the complex dynamic viscosity η ^* (1) in seconds and the complex dynamic viscosity η ^* (100) at a frequency of 100 radians / second is 0.67 or less. Thermoplastic elastomer powder. ^{n = {logη * (1)} -logη * (100)} / 2