JP3212403B2 - Laminating sheet and method for producing laminated molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to interior parts for automobiles, housings for office automation equipment and home appliances, stationery, sanitary goods, daily necessities, interior parts for construction, etc.
More specifically, the present invention relates to a method for manufacturing a laminated molded product that can be touched by a human, and more particularly, to a laminated sheet having a soft touch layer used for producing a laminated molded product having a coating layer having a soft touch feeling (suede-like). And a method for producing the laminated molded article.

[0002]

2. Description of the Related Art In order to impart a suede feeling (soft touch feeling) to the surface of a molded article such as a plastic molded article or a metal molded article, a suede tone (soft touch) is generally used.
Paints have been used. However, when a suede-like film is formed using a paint, it is necessary to adjust the viscosity and the concentration of the paint, and the operation becomes complicated. A coating using an organic solvent requires a booth to dry the solvent, and further causes pollution of the working environment and safety and health problems.

In order to solve these problems, a sheet-like suede-like coating material has been proposed in place of paint.
For example, Japanese Unexamined Patent Publication (Kokai) No. 2-41243 discloses a matte paint obtained by adding a bead pigment to a vehicle of an ionizing radiation-curable resin, and applying the matte paint on a base film having good moldability and curing. A seat has been proposed.

[0004]

However, since the above-mentioned conventional sheet is formed by providing a resin layer cross-linked by an electron beam on a base film such as ABS resin or polypropylene, the spreadability of the entire sheet is increased. For example, when a molded article having irregularities or a curved surface is covered with a sheet, there is a drawback that it is difficult to apply the sheet while stretching, and it is difficult to impart a sufficient suede feeling. .

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to apply a molded article having irregularities or curved surfaces while stretching the sheet, and in particular, irregularities in which a sheet is stretched. Provided is a method for producing a laminated molded article using a laminating sheet capable of forming a suede-like coating that does not cause a decrease in appearance or soft touch feeling by stretching even at a curved surface portion or the like, and a sheet for the lamination. Is to do.

[0006]

According to the present invention, there is provided a laminating sheet comprising a thermoplastic polyurethane, elastic fine particles or oil absorbing material.
100-400ml / 100g porous inorganic fine particles
And a composition containing a pyrolytic foaming agent.
Was has a source Futotatchi layer obtained by the above objects can be achieved.

[0007] method of manufacturing a multilayer molded article of the present invention, the thermoplastic
Polyurethane and elastic fine particles or oil absorption of 100
~ 400 ml / 100 g of porous inorganic fine particles and heat component
The composition containing a demolding foaming agent is obtained by heating and foaming.
The laminating sheet having Luso Futotatchi layer, such that the soft touch layer is on the surface side of the molded article, and the sheet was introduced molding resin step is arranged in the mold, and the mold And an integrating step, whereby the object is achieved.

(Soft Touch Layer) It is presumed that the soft touch feeling in the present invention is caused by the low surface contact resistance due to the fine irregularities on the sheet surface, which results in a smooth feel. This effect is also useful for controlling the light reflectance of the surface by forming fine irregularities, that is, for controlling the gloss. Therefore, the soft touch layer formed on the laminating sheet means a resin foam layer of a predetermined thickness having such a soft touch feeling on the surface. The fine unevenness is caused by the fact that elastic fine particles and / or porous inorganic fine particles are blended in the sheet as described later, and the fine unevenness usually has a size of 1 to 50 μm.

The soft touch layer of the laminating sheet of the present invention comprises a thermoplastic polyurethane and elastic fine particles or
Porous inorganic material with oil absorption of 100-400ml / 100g
A composition containing fine particles and a pyrolytic foaming agent is heated and heated.
The thermoplastic polyurethane formed by foaming
Formed by dispersing elastic fine particles or porous inorganic fine particles in the foamed layer.

[0010] As the above-mentioned thermoplastic polyurethane, thermosetting polyurethane is used.
Plastic urethane resin and thermoplastic urethane elastomer
Is used.

[0011] Here, <br/> a thermoplastic urethane elastomer, at room temperature show a so-called rubber elasticity at high temperatures intends words the polymeric material capable molded of plasticized Various.

In general, thermoplastic urethane elastomers often share a rubber component (soft segment) having entropy elasticity in a molecule and a molecular constraint component (hard segment) for preventing plastic deformation, and can be molded. In some cases, it may have a partially crosslinked structure, but does not have a wide-range three-dimensional network crosslinked structure.

[0013] The hardness of these thermoplastic urethane elastomers, and feel to be obtained varies depending hardness of fine particles composed of natural polymer to be used is generally JIS
Is used et <br/> Re that the range of 20 to 98 at A hardness K6301.

[0014] The onset Ming laminating sheet is a casting method, the reaction film forming method, the thermoplastic Poriu by extrusion or the like
It can be prepared urethane composition or al. For example, in the casting film forming method as an example , thermoplastic
Urethane resins (hereinafter, simply referred to as urethane resin.)
About described in more detail below.

The urethane resin has a glass transition point (T) in order to impart a soft touch feeling and abrasion resistance to the laminating sheet.
g) in the range of -50 ° C to 20 ° C is preferred. When a urethane resin having a glass transition point of less than −50 ° C. and a urethane resin exceeding 20 ° C. are used, the soft touch feeling becomes poor.

The urethane resin is classified into a straight-chain type (high-molecular-weight type) and a cross-linked type (reactive film-forming type), and any of them can be used.

When a straight-chain type urethane resin is used, a method of forming a sheet for lamination by forming a film of the resin composition as it is by a casting method, and a method of forming a sheet for lamination by polymerizing at the time of casting film forming are used. is there. When a crosslinked urethane resin is used, it is preferable to form a sheet by the latter method.

Such a urethane resin is usually obtained by reacting a diisocyanate, a diol and a chain extender. Examples of the diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Methyl xylylene diisocyanate, trimetrhexamethylene diisocyanate, and the like. Examples of the diol include polyester diols (condensed polyester diol, lactone-based polyester diol, polycarbonate diol, and the like), and polyether diols. , Ethylene glycol , 1,4-butanediol, hydroquinone diethylcarbamoyl roll ether, and the like.

When a sheet is produced by casting, the above-mentioned material can be polymerized in advance in a solution to obtain a urethane resin (a catalyst such as dibutyltin dilaurate may be added to promote this reaction). ). In this case, the urethane resin has a weight average molecular weight in the range of 20,000 to 3,000,000, particularly 20,000 to 1,000,000.
Are preferred. If the weight average molecular weight is less than 20,000, the sheet tends to crack when the sheet is spread. When the weight average molecular weight exceeds 3,000,000, it becomes difficult to dissolve the resin in the solvent.For example, when a sheet is prepared by solvent casting, the viscosity of the solvent becomes high, so that the resin can be cast only at a low concentration. Significant costs will be involved in creating the sheets. When the urethane resin material is polymerized at the time of casting, the above-mentioned low molecular weight material or a polymerized material thereof is used, and further, a bifunctional isocyanate is added and polymerized by heat at the time of film formation to form a sheet for lamination. Can be created.

When a sheet is prepared using a crosslinked type (reaction film forming type) urethane resin, a low molecular material or a polymerized polymer material thereof is used in the same manner as in the case of polymerizing at the time of casting described above. Further, a laminating sheet may be prepared by adding at least trifunctional or higher functional isocyanate and polymerizing with heat during film formation. These at least trifunctional or higher isocyanates are added as far as the sheet can be spread (curved surface followability). Examples of such an isocyanate include an isocyanurate of hexamethylene diisocyanate and an adduct of trimethylolpropane. By using the urethane resin partially crosslinked as described above, the solvent resistance of the lamination sheet can be improved. Further, a melamine crosslinking agent may be used in addition to the isocyanate. The addition amount of each of these materials, that Re <br/> made within the proper range of the melt viscosity during sheet forming.

The elastic fine particles contained in the thermoplastic polyurethane have a property of recovering elasticity when they are released after being pressed until their shape is deformed, and are, for example, polyurethane, acrylic-urethane copolymer , cross-linked. Polyacrylic
Acid ester (for example, EAX-2 manufactured by Sekisui Plastics Co., Ltd.)
0), styrene-isoprene copolymer and the like. These elastic beads having a maximum particle size distribution in the range of 1 to 50 µm are generally used in an amount of 20 to 200 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the polyurethane.
0-150 parts by weight are added. The particle size of the elastic fine particles is 1 μm
If the average particle size is less than the above range, a sufficient suede feeling (soft touch feeling) cannot be obtained in the obtained sheet, and the particle size of the elastic fine particles is 50 μm.
When the ratio exceeds the above, cracks tend to occur on the surface of the sheet when the sheet is stretched. If the amount of the elastic fine particles is less than 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin, a sufficient suede feeling (soft touch feeling) cannot be obtained on the sheet. In addition, cracks are easily formed on the surface. The number of the elastic fine particles is not limited to one type, and two or more types may be used in combination.

The porous inorganic fine particles contained in the thermoplastic polyurethane include, for example, hydrous silicic acid (SiO ₂
XH ₂ O) or hydrous aluminum silicate (Al ₂ O _3.
9SiO ₂ · xH ₂ O) and natural diatomaceous earth, and the like. What is generally called white carbon is preferably used. The water preferably contains 1 to 10% by weight. These inorganic fine particles have an average particle size of 30 μm.
The following are preferred, and more preferably 1 to 20 μm
It is. When the particle diameter is larger than 20 μm, the surface of the obtained soft touch layer becomes uneven, so that it is difficult to obtain an excellent soft touch feeling, and cracks are liable to be generated on the surface when the sheet is stretched or stretched.

The porous material has a numerical value called oil absorption. This varies depending on the nature of the thermoplastic polyurethane Ru using, for example, thermoplastic polyurethane and porous thermoplastic If compatibility is good and material Poriu of Ru with
Since a large amount of urethane is retained in the porous material, the oil absorption is 1
Use the one of 00 to 400 ml / 100 g. Oil absorption
If it is less than 100 ml / 100 g, it is necessary to add a large amount of porous inorganic fine particles to make the sheet surface uneven, so that the coating film becomes hard and an excellent soft touch feeling cannot be obtained.

Therefore, the addition amount of the porous inorganic fine particles is
Although it varies depending on the thickness of the obtained sheet, for example, when a sheet having a thickness of 100 μm is obtained, when the above-mentioned porous inorganic fine particles are used , the above-mentioned thermoplastic polyurethane 10 is used.
It is preferable to add 10 to 40 parts by weight to 0 parts by weight. If the addition amount is less than 10 parts by weight, the surface of the soft touch layer cannot be made sufficiently uneven, and an excellent soft touch feeling (slip feeling: decrease in friction coefficient) cannot be obtained. If the amount of addition is large, cracks are likely to be generated on the surface during sheet stretching. These porous inorganic fine particles are not limited to one kind, and two or more kinds may be used in combination. These porous inorganic fine particles and elastic beads may be added at the same time.

[0025] The thermoplastic polyurethane foam layer is contained in the pyrolysis-type in order to form a (soft touch layer)
A chemical blowing agent is used. Thermal decomposition type chemical blowing agent
It is easy to make air bubbles fine and good in obtaining suede tone.
Suitable. The thermal decomposition type chemical blowing agent is described below.
I do.

[0026] The thermal decomposition type chemical foaming agent, azo, hydrazo type, semicarbazide, hydrazone, triazole, and the like N- nitroso. Examples of these include azodicarbonamide, barium azodicarboxylate, azobisisobutyronitrile, hydrazodicarbonamide,
Isopropyl hydrazodicarboxylate, p-toluenesulfonylhydrazide, acetone-p-toluenesulfonylhydrazone, p, p'-oxybis (benzenesulfonylhydrazide), dinitrosopentamethylenetetramine, trihydrazinotriazine, 5-morpholinyl-1,2,3, There are 4-thiadriazole and 5-phenyltetrazole.

[0027] These foaming agents, thermoplastic Poriu to use
Depending on the physical properties of the urethane, it is appropriately selected in consideration of the decomposition temperature, generated gas amount, gas composition and the like. The preferred expansion ratio of the soft touch layer is up to 1.2 to 6 times, more preferably 2 to 4 times.
Up to double. These amount of blowing agent is generally thermoplastic is
For sexual polyurethane, 0.1 to 10% by weight, preferably 0.2 to 3 wt%.

[0028] If necessary, a material such as a coloring agent such as a pigment or a dye or an antioxidant may be added to the thermoplastic polyurethane . Pigments and dyes used in paints can be used as the coloring agent. Examples of pigments include titanium oxide, iron oxide, carbon black, cyanine pigments, and quinacridone pigments. As dyes, azo dyes, anthraquinone dyes,
There are indigoid-based dyes, stilbene-based dyes, and the like.
Further, metal powder such as aluminum flake, nickel powder, gold powder and silver powder may be used as the coloring agent. These materials are preferably fine particles as much as possible. When a coloring agent having a high concealing property is used, the amount of these additives is limited to the thermoplastic resin.
The range of 2 to 40 parts by weight is preferably based on 100 parts by weight of the solid content of the urethane . However, when these colorants are added, the soft touch feeling imparted by the elastic fine particles, the porous inorganic fine particles, and the like may be different, so the amount of the elastic fine particles and the porous inorganic fine particles changes in the system to which the colorant is added. Sometimes.

In order to impart various functions to the sheet for lamination of the present invention, various functional imparting materials may be added. Examples of the above-mentioned various function-imparting materials include known conductive materials, anti-condensation agents, photochromic compounds, rust inhibitors and the like.

(Adjustment of Laminating Sheet) The laminating sheet may be prepared by any method such as a casting method, a laminating method, an extrusion method and a calendering method.

When the laminating sheet is a single layer, the following casting method is preferred.

The thermoplastic polyurethane composition is sufficiently dissolved or dispersed in an organic solvent. The resulting solution is coated on process paper (usually a polyethylene terephthalate film or paper whose surface has been treated with silicone) using equipment such as a knife coater, bar coater or reverse coater, and then used for solvent removal and foaming. To form a base layer. By peeling the process paper from the base layer, a sheet is obtained.

When the laminating sheet is formed of a plurality of layers, it can be obtained by a casting method or a laminating method. According to the casting method, a solution containing the thermoplastic polyurethane composition of either one of the layers is coated on the process paper as described above, and a layer is formed by performing heating for removing the solvent and for foaming.
A solvent containing the thermoplastic polyurethane composition of the other layer is coated on this layer, and heating for removing the solvent and foaming is performed to form another layer. Or AB
Thermoplastic resin on a layer such as S-resin or polycarbonate
A solvent containing the urethane composition is coated and heated to form a layer. According to the lamination method, a solution containing the thermoplastic polyurethane composition of each layer is separately applied to process paper, heated to form each layer, and then both layers are laminated and (heated) by a roll press. Press to obtain a sheet. At this time, an adhesive layer may be laminated between the two layers to improve the adhesion. The process paper used in the production can be used as a protective sheet. The heating temperature for the foaming is determined by the foaming agent used,
Generally, the temperature is from 120C to 250C.

The time for foaming the soft touch layer is usually performed when the sheet is formed as described above. However, by suppressing the heating temperature, the unfoamed thermoplastic resin is formed.
Forming a sexual polyurethane composition layer, then, for example, soft touch <br/> by foaming by Rinetsu thermoplastic polyurethane composition layer to heating at a high temperature after being spread adhesion resin layer in a mold surface A layer may be formed.

[0035] (laminating aspect of Sheet) above thermoplastic polyurethane composition or al, soft touch layer (base layer) is created by the method described above, when the sheet is a single layer, the soft touch layer Is a sheet for lamination as it is, and when the sheet is composed of a plurality of layers, for example, the following forms are available.

A sheet having a base layer and a back surface layer laminated on the back surface of the base layer.

The back layer is used to further improve the handleability of the sheet, to improve the adhesion between the laminating sheet and the resin for injection molding when the sheet is used for injection molding, It is provided to reinforce the resin to withstand the shear stress of the resin.

The resin forming the back surface layer and the resin for injection molding are preferably the same or excellent in compatibility.
When the adhesion between the base layer and the back layer is poor, a primer layer may be provided between both layers, and a plurality of back layers may be provided.

Since the laminating sheet of the present invention is stretched and attached to an adherend as required, the back layer (and the primer layer) is composed of a film having spreadability at room temperature or at least under heating. Is preferred.

The resin used for the back layer is, for example, a thermoplastic resin used for the base layer, polystyrene,
Acrylic polymers, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, ABS copolymer (acrylonitrile-butadiene-styrene copolymer), modified polyphenylene oxide, polyphenylene sulfide, polyetherimide, polyetheretherketone, ionomer, and the like. .

In some cases, a pattern such as gravure, silk screen, printing by offset, or the like is applied to these back layers. Further, a foam layer may be provided on these back layers (in some cases, only the base layer). Examples of the material forming the foam layer include foamable resin materials such as polyethylene, polypropylene, polystyrene, urethane resin, polyvinyl chloride, and various thermoplastic resin resins. The foaming ratio of these foam layers is to further develop a soft touch feeling on the sheet.
Those having 5 to 50 times, preferably 20 to 50 times are preferably used.

A base layer or the sheet obtained above,
A sheet having an adhesive layer laminated on one side of the sheet (the outer surface of the back layer in the case of the sheet).

As the adhesive used for the adhesive layer, a pressure-sensitive adhesive, a hot-melt adhesive, and a post-curing adhesive are preferably used. Mixtures of these adhesives may be used. When good adhesiveness cannot be satisfied with one type of adhesive due to the materials of the sheet and the adherend, a plurality of different types of adhesive layers may be sequentially laminated. The primer layer is used according to the properties of the resin to be laminated. For example, a chlorinated polyolefin such as chlorinated polypropylene can be used.

The pressure-sensitive adhesives include, for example, pressure-sensitive adhesives of rubber type, acrylic type, silicone type and the like. Examples of the hot melt adhesive include an ethylene-vinyl acetate copolymer (EVA) and a styrene-isoprene-styrene block copolymer (SIS). Examples of the post-curing adhesive include a microcapsule curing adhesive, and examples of the material include an uncrosslinked unsaturated polyester-based adhesive and an uncrosslinked acrylic adhesive.

A sheet comprising the above sheets and a protective layer laminated on the surface of the sheet.

The protective layer is laminated in order to provide shape retention during storage and use of the sheet and surface protection after application. Since the laminating sheet of the present invention is stretched and attached to an adherend as necessary, it is preferable that the protective layer is formed of a film (for example, a thermoplastic resin film or a rubber film) having at least extensibility under heating.

The thermoplastic resin includes, for example, soft vinyl chloride, polyurethane, acrylic resin, polyester, ethylene-vinyl acetate copolymer, polyethylene, polypropylene and the like. Examples of the rubber include natural rubber, styrene butadiene rubber, nitrile butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, urethane rubber, silicone rubber, acrylic rubber, and the like. These thermoplastic resins and rubber mixtures can also be used. Alternatively, both films may be laminated.

The protective layer may be peeled off from the adherend immediately after the sheet is adhered to the adherend, and then the sheet may be cured, or after the sheet is adhered to the adherend and cured. It may be used as a protective layer until the adherend is used. If you add embossing or patterns to the surface of the protective layer,
The surface shape (appearance) of the sheet can be changed.

A sheet having a transparent base layer (surface layer) and a coloring layer containing a coloring agent.

The colored layer can be formed from the resin composition used for the base layer. In this case, the coloring layer may not contain a porous inorganic material or elastic beads.

A sheet in which the surface or the back surface of the base layer of the above-mentioned sheets is patterned by printing or the like performed by gravure, silk screen, offset or the like.

The thickness of the laminating sheet of the present invention thus obtained is preferably about 20 to 1,000 μm when sticking to an uneven adherend surface, and 5 to 500 μm when sticking to a flat surface. It does not matter. When a foam layer is further provided, the thickness of the foam layer is preferably 1 to 5 mm. In particular, the thickness of the adhesive layer (primer layer) is 2 to 100 μm.
m is preferred.

(Method of Manufacturing Laminated Molded Article) The method of manufacturing a laminated molded article according to the present invention is to arrange a laminating sheet in a mold, perform pneumatic molding, for example, and then introduce a resin into the mold. The molding is performed in a batch system, and examples thereof include injection molding, stamping molding, press molding, and sheet molding.

Typically, the laminating sheet of the present invention is melted and adhered to the mold surface provided on the female mold by pneumatic molding, that is, vacuum and / or pneumatic molding, and then the resin is injected into the mold. A laminated molded article is manufactured. In particular,
There are the following methods.

1) When performing injection molding or stamping molding, the laminating sheet is previously disposed in a mold so as to face the surface side of the molded article from which the soft touch layer of the sheet is obtained, and the molding resin is molded. At the same time, the sheet is attached to the molded product.

Thereafter, at the time of stamping molding, the molding resin is introduced into the mold, and then the mold is closed. At the time of injection molding, the mold is closed, and then the resin is introduced to obtain a laminated molded product.

2) When performing injection molding, the laminating sheet is preliminarily formed by pneumatic molding into the shape of a female mold surface, and then temporarily removed from the mold surface. The resulting molded product is introduced into a mold so as to face the surface side. Thereafter, the mold is closed and the resin is introduced to obtain a laminated molded product.

The above-mentioned pneumatic forming means vacuum forming, compressed air forming and the like. The preliminary molding may be performed using a mold for molding a resin such as injection molding, or another mold for sheet molding may be used. In this case, after introducing the preformed sheet into a mold for injection molding, etc.,
Molding such as injection molding is performed.

As the molding resin used in the above, any material can be used as long as it is a material usually molded. For example, ABS resin (acrylonitrile-butadiene-styrene copolymer), polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, acrylic resin, polyetherimide, polyphenylene sulfide, nylon, and the above-mentioned thermoplastic elastomer, These materials include those having glass fibers and inorganic fillers.

Further, using the lamination sheet of the present invention,
For example, a laminated molded product can be manufactured continuously by extrusion molding, drawing molding, or the like. In these methods, a method for introducing a sheet for lamination into a mold and attaching it to a molded product simultaneously with continuous molding, a method for attaching the sheet for lamination immediately after the molded product comes out of the mold, and before sizing, a method for sizing , After cooling. In the method of introducing a sheet for lamination into a mold, the method is performed such that the sheet for lamination is wound in front of or in the middle of the mold. In the method of attaching a laminating sheet after molding (directly), the laminating sheet is adhered by a pressure roller along the surface of the molded product. In vacuum (pressure) molding, the laminating sheet of the present invention is laminated on a sheet to be molded in advance, and is performed by a normal method.

Attaching to a long member such as wood or aluminum sash is performed by a commercially available profile laminator or the like. At this time, it is preferable to provide an adhesive layer in order to improve the adhesion to the adherend. The laminating sheet on which the pressure-sensitive adhesive is laminated is pasted to the molded product by hand or a double vacuum forming machine (pasting machine).

(Use of Laminating Sheet) The laminating sheet of the present invention is intended to impart a soft touch to the surface of a product, and thus is mainly used for coating a molded product which is touched by a human. .

For example, instrument panels, handlebars, gear lever knobs, door knobs, door trims, armrests, various switches, seats, ceiling materials, etc. as automobile interior parts; portable products (telephones, cassette tape recorders, Compact discs, televisions, etc.), telephones, refrigerators, televisions, etc. and their respective switches, etc .; OA product housings, personal computers, printers, keyboards, etc .; furniture products, chairs, desks, tables, clothes dances, etc .; Sash frame, parquet, various doors, wallpaper, etc.
Sanitary, bathroom products, toilet seat stool, bathtub, chairs, mats, shelves, etc .; sports equipment, bats, rackets, clubs, etc. grips, protective pads, etc .;
As daily necessities and stationery products, various housings, cases, containers, etc .; benches, chairs, stands, sofas, etc.
Pillows and the like;

[0064]

[Action] laminated sheet of the present invention, also is properly elastic fine particles
Multi-porous inorganic fine particles oil absorption of 100~400ml / 100g is, because it has a soft touch layer is dispersed in the thermoplastic polyurethane by Li Cheng foam layer, just Paste the sheet to the substrate surface, easily In addition, it is possible to obtain a laminated molded product having a soft touch feeling caused by fine irregularities on the surface.

When this laminated sheet is used, a film having a uniform appearance is formed even in the production of a laminated molded article having irregularities in order to prevent a change in appearance and a decrease in soft touch feeling even in a stretched portion of the sheet. It becomes possible.

[0066] In particular, the soft touch layer foamed layer or Rannahli, because the compression modulus is less than the case of non-foamed layer, in addition to the soft touch feeling caused by the unevenness due to the fine particles, the foam layer The resulting soft touch feeling can be further imparted to the surface of the molded product.

[0067]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments.

In the following examples, "parts" means "parts by weight" in solid content unless otherwise specified.

(A) Preparation of sheet for lamination (Example 1) Urethane resin (Nipporan 5120, manufactured by Nippon Polyurethane Industry Co., Ltd., non-yellowing type, polyester type, Tg =
−33 ° C., Mw = 100,000, solid content 30%) 10
0 parts elastic fine particles (Nippon Shokubai Chemical Co., Ltd., EBS300, acrylic-urethane elastic beads, average particle size 30 μm) 12
0 parts Carbon black 4 parts Blowing agent (manufactured by Sankyo Kasei Co., Ltd., Cell Mike 172-C, azo type) 2 parts The above components were mixed with stirring.

The resulting mixture was treated with a primer-treated olefin-based thermoplastic elastomer sheet (film thickness 400
μm, prepared by calender molding)
For 5 minutes, and further heated at 165 ° C. for 5 minutes to form a foamed soft touch layer (2.0 times expansion ratio) to obtain a sheet for lamination. The thickness of the soft touch layer of the obtained laminate sheet was 100 μm.

(Example 2) Urethane resin (manufactured by Nippon Polyurethane Industry Co., Ltd., SH7
03, non-yellowing type, polycarbonate, solid content 30
%) 100 parts elastic fine particles (UB15 (black), urethane elastic beads, average particle size 22 μm, manufactured by Sekisui Chemical Co., Ltd.) 7
0 parts foaming agent (manufactured by Sankyo Kasei Co., Ltd., cell microphone M3013, azo type) 1 part A sheet for covering was obtained. The thickness of the soft layer of the obtained sheet for lamination was 50 μm. The above was mixed with stirring.

The obtained mixture was applied by gravure printing onto an olefin-based thermoplastic elastomer sheet (thickness: 400 μm, formed by calendering) on which a stone pattern was printed, and dried at 80 ° C. for 5 minutes. 5 at 170 ° C
By heating for a minute, a foamed soft touch layer (expansion ratio: 1.5 times) was formed to obtain a sheet for lamination. The thickness of the soft touch layer of the obtained sheet for lamination was 50 μm.

(Example 3) 100 parts of urethane resin (Nipporan 5230, non-yellowing type, polycarbonate type, solid content 30%, manufactured by Nippon Polyurethane Industry Co., Ltd.) isocyanate (Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.) 2 parts Curing catalyst (dibutyltin dilaurate) 0.5 part Elastic fine particles (manufactured by Nippon Shokubai Chemical Industry Co., Ltd., EBS100, elastic beads of acryl-urethane, average particle diameter 10 μm) 80
Part 1 part foaming agent (manufactured by Sankyo Kasei Co., Ltd., CellMike MB2022, azo type) 1 part or more were mixed with stirring.

The obtained mixture is applied by gravure printing onto an olefin-based thermoplastic elastomer sheet (thickness: 1000 μm, prepared by calendering) on which a stone pattern is printed, and dried at 80 ° C. for 5 minutes. By heating at 180 ° C. for 5 minutes, a foamed soft touch layer (foaming ratio: 3 times) was formed to obtain a laminate sheet. The thickness of the soft touch layer of the obtained sheet for lamination was 50 μm.

Example 4 A urethane resin (manufactured by Nippon Polyurethane Industry Co., Ltd., SH703)
Non-yellowing type, polycarbonate type, solid content 30
%) 100 parts elastic fine particles (manufactured by Sekisui Plastics Co., Ltd., elastic beads of EAX-20 crosslinked polyacrylic acid ester, average particle size 20 μm)
m) 80 parts Foaming agent (Serkyo Kasei Co., Ltd., Cell Mike MB2022) 1 part The resulting mixture is coated on a primer-treated olefin-based thermoplastic elastomer sheet (thickness 400 μm, prepared by calendering). After drying at 80 ° C. for 5 minutes and heating at 170 ° C. for 5 minutes, a foamed soft touch layer (expansion ratio 1.5 times) was formed, and a polypropylene foam sheet (film thickness 2 mm, expansion ratio 2)
5 times) on the back surface of the olefin-based elastomer sheet. The thickness of the soft touch layer of the obtained laminate sheet was 100 μm.

Example 5 100 parts of a urethane resin (Nipporan 5230, non-yellowing type, polycarbonate type, solid content 30%, manufactured by Nippon Polyurethane Industry Co., Ltd.), a porous inorganic material (manufactured by Fuji Devison Chemical Co., Ltd.) Syloid 244, hydrated silicate, average particle size 1.8 μm, oil absorption 310 ml / 100 g) 5 parts Elastic fine particles (manufactured by Nippon Shokubai Chemical Industry Co., Ltd., EBS300, acrylic-urethane elastic beads, average particle size 30 μm) 70
Part: 2 parts of a foaming agent (manufactured by Sankyo Kasei Co., Ltd., Cell Mike 172-C, azo type).

The resulting mixture was treated with a primer-treated olefin-based thermoplastic elastomer sheet (thickness: 400).
μm, prepared by calender molding)
For 5 minutes, and further heated at 165 ° C. for 5 minutes to form a foamed soft touch layer (expansion ratio 2 ×). Further, a polypropylene foam sheet (film thickness 2 mm, expansion ratio 25 ×) was added to the elastomer sheet. The back was heat-laminated. The thickness of the soft touch layer of the obtained laminate sheet was 100 μm.

(Comparative Example 1) Soft touch paint (Cenosoft II, manufactured by Cashew Co., Ltd.) on an olefin-based thermoplastic elastomer sheet (400 μm thick, prepared by calender molding) on which a stone pattern was printed by gravure printing Was applied and cured by heating at 80 ° C. for 30 minutes to form a soft touch layer having a coating thickness of 50 μm to obtain a sheet for lamination. The thickness of the obtained sheet for lamination was 50 μm.

Comparative Example 2 A polypropylene foam sheet (film thickness: 2 mm, foaming ratio: 25 times) was formed on an olefin-based thermoplastic elastomer sheet (film thickness: 400 μm, prepared by calender molding) on which a stone pattern was printed by gravure printing. ) Was heated and laminated to obtain a sheet for lamination.

(B) Method for Producing a Laminated Molded Product (B) -1 Injection Molding The laminated sheets obtained in Examples 1, 2, and 3 and Comparative Examples 1 and 2 are shown in FIGS. Injection molding was performed by an injection molding apparatus according to the method described below to obtain a laminated molded product.

This injection molding apparatus is provided with a molding recess 20a.
Mold 20 having a vent 20b for drawing air and vacuum
And a fixed mold 22 having a convex portion 22a;
A hot platen 24 having a hole for vacuum and compressed air, which is disposed between the molds 22 and is movable outside from between the two molds 20, 22.
And a resin injection machine 25.

First, as shown in FIG.
0 and the hot platen 24, the sheet 23 for lamination is introduced, and the sheet 23 is heated while being sucked by the hot platen 24, so that the sheet 2
3 is transferred to a moving mold 20 by vacuum and / or pressure forming.
(The concave portion 20a). Next, as shown in FIG. 3, the hot platen 24 is moved outward from between the two dies 20, 22, and then the movable dies 20 are moved to the fixed dies 22 to close the dies. Next, a molding resin was injected from the resin injection machine 25 into the cavity formed by the two dies 20 and 22 at a nozzle tip temperature of 230 ° C. The resin used is polypropylene (BC3, manufactured by Mitsubishi Yuka Co., Ltd.). After molding, the molded product was taken out of the mold to obtain an injection molded product.

The evaluation of the soft touch feeling was as follows.
A sensory test was conducted by touch when a human paneler touched the surface of the molded product with a hand.

Panelists: 10 males and females aged 15 to 40 years old 1 point: Not soft touch 2 points: Not slightly soft touch 3 points: Soft touch

[0085]

[Table 1]

For the sheet of Comparative Example 1, the molding temperature 1
The compressed air vacuum forming was performed at 40 ° C., but cracks occurred at the sheet corners, and forming was impossible.

For Comparative Example 2, the soft touch feeling on the foam sheet side was tested.

(B) -2 Stamping Molding Using the lamination sheets obtained in Examples 4 and 5, stamping molding was performed according to the following method.

As shown in FIGS. 5 to 8, this molding machine
It has an upper mold 1, a lower mold 2, and a resin injection machine 6. A convex portion 11 is provided on the lower surface of the upper die 1, and a concave portion 21 is provided on the upper surface of the lower die 2 at a position corresponding to the convex portion 11. A resin injection path 26 is formed at the center of the lower mold 2, and a nozzle 61 of the resin injection machine 6 is provided in the resin injection path 26.

As shown in FIG. 6, the sheet 3 is introduced between the upper mold 1 and the lower mold 2 heated to a predetermined temperature, and the periphery of the sheet 3 is fixed around the periphery of the lower mold 2 with the fixing pins 4. did. Next, as shown in FIG. 7, the molding resin 5 was injected from the nozzle 61 of the resin injection machine 6 into the lower mold 2 at a nozzle tip temperature of 230 ° C. The resin used was polypropylene (Mitsubishi Yuka Corporation)
BC3).

Next, as shown in FIG. 8, the upper mold 1 was closed at a predetermined pressure to form the sheet 3 and the resin 5 was stamped to obtain a laminated molded article having the shape shown in FIG. 8 and 9, L1 is 200 mm, L2 is 300 m
m, L3 is 30 mm, L4 is 150 mm, L5 is 280
mm, L6 is 60 mm, and L7 is 500 mm. Table 2 shows the preheating temperature of the sheet, the appearance of the obtained laminated molded product, and the soft touch feeling in each example.

[0092]

[Table 2]

[0093]

The laminating sheet of the present invention is excellent in extensibility, so that not only when it is formed into a flat article but also when a molded article having irregularities or curved surfaces is formed, cracking does not occur and a soft touch feeling is obtained. (Suede-like) coating can be formed on the surface of the molded article. In particular, since a foam layer having a low compression modulus can be formed on the surface, the soft touch feeling can be further increased.

Therefore, there is an advantage that conventional problems of coating space and environmental problems such as solvents are eliminated, and decoration of various plastic molded bodies such as housings and stationery of office automation equipment and home appliances can be easily and inexpensively performed. There are advantages. Further, according to the method for producing a laminated molded product of the present invention, there is an advantage that the production of these laminated molded products is extremely easy, and therefore, it can be performed at low cost.

[Brief description of the drawings]

FIG. 1 is a front view of an injection molding machine used in an embodiment of a method of manufacturing a laminated molded product according to the present invention, showing a state where a movable mold and a fixed mold are separated.

FIG. 2 is a partially cutaway front view of an injection molding machine used in one embodiment of the method for producing a laminated molded product of the present invention, showing a state in which a laminating sheet is sucked on a hot platen.

FIG. 3 is a front view of an injection molding machine used in one embodiment of the method for producing a laminated molded product according to the present invention, showing a state in which a laminating sheet is brought into close contact with an inner surface of a concave portion of a movable mold.

FIG. 4 is a front view of an injection molding machine used in an embodiment of the method for manufacturing a laminated molded product according to the present invention, showing a state in which a mold is closed and a molding resin is injected from a resin injection machine into a cavity. Show.

FIG. 5 is a sectional view of a stamping molding machine used in another embodiment of the method of manufacturing a laminated molded product according to the present invention, showing a state where an upper mold and a lower mold are separated.

FIG. 6 is a cross-sectional view of a stamping molding machine used in another embodiment of the method of manufacturing a laminated molded product according to the present invention, showing a state where a sheet is arranged on a lower mold.

FIG. 7 is a cross-sectional view of a stamping molding machine used in another embodiment of the method of manufacturing a laminated molded product according to the present invention, showing a state in which a resin is introduced into a concave portion of a lower die.

FIG. 8 is a cross-sectional view of a stamping molding machine used in another embodiment of the method of manufacturing a laminated molded product according to the present invention, and shows a state in which a resin is stamped and molded.

FIG. 9 is a cross-sectional view of a laminated molded product obtained by stamping as a method for producing a laminated molded product of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 upper die 2 lower die 5 molding resin 6 resin injection machine 11 convex portion 20 moving die 20a, 21 concave portion 22 fixed die 23 laminating sheet 24 hot platen 25 resin injection machine 26 resin injection path 61 nozzle

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 C08J 9/00-9/42 C08J 11/00-11/28

Claims (2)

(57) [Claims] (1) thermoplastic polyurethane and elastic fine particles
Or porous with oil absorption of 100-400ml / 100g
A composition containing inorganic fine particles and a pyrolytic foaming agent
Laminating sheet having a source Futotatchi layer obtained by heating and foaming. 2. A thermoplastic polyurethane and elastic fine particles
Or porous with oil absorption of 100-400ml / 100g
A composition containing inorganic fine particles and a pyrolytic foaming agent
The laminating sheet having a source Futotatchi layer obtained by heating and foaming, as the soft touch layer is on the surface side of the molded article, introducing molding resin step is arranged in the mold, and the mold And integrating the sheet with the sheet.