JPH04345666A - Covering sheet - Google Patents

Abstract

PURPOSE:To provide a covering sheet which exhibits a desirable hand simply at a low cost by forming the sheet from a resin compsn. comprising mainly elastic beads and/or an inorg. porous material and a resin such as an acrylic resin. CONSTITUTION:Elastic beads (e.g. cross-linked polystyrene beads) and/or an inorg. porous material (e.g. hydrated silicic acid), at least one resin selected from the group consisting of an acrylic resin, a fluororesin, and a silicone resin, and, if necessary, an additive such as a pigment or an antioxidant are mixed to give a resin compsn., which is formed into a covering sheet by e.g., casting or laminating. The sheet, excellent in extensibility, can be adhesively bonded to an uneven or curved surface of an article, thus forming a solvent- and scratch-resistant surface-covering layer having an excellent soft hand.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is applicable to automobile interiors, OA
Housings for equipment and home appliances, stationery, sanitary products, etc.
The present invention relates to a covering sheet that can be applied to areas that are likely to be touched by people, such as daily necessities and architectural interiors, to impart a pleasant tactile sensation to the areas.

0002

BACKGROUND OF THE INVENTION Soft-touch (suede-like) paints have generally been used to impart a soft-touch feel (suede-like feel) to the surfaces of plastic molded bodies, metal molded bodies, and the like.

However, when forming a suede-like coating using a paint, it is necessary to adjust the viscosity and concentration of the paint, which makes the work complicated. Paints using organic solvents require booths, contaminate the work environment, and pose health and safety problems.

[0004] In order to solve these problems, a sheet-like suede-like coating material has been proposed in place of paint. For example, JP-A No. 2-41243 discloses a suede-like product in which a matte paint obtained by adding bead pigments to a vehicle of ionizing radiation-curable resin is applied onto a base film with good formability and cured. sheet is proposed.

[0005]

[Problems to be Solved by the Invention] However, in such suede-like sheets, the coating film is made of a resin crosslinked by electron beams, so the spreadability of the entire sheet is poor. Therefore, for example, even if you try to attach a sheet to the surface of an adherend that has unevenness or a curved surface, the sheet cannot be stretched sufficiently, so the sheet may tear, and especially deep-drawn products with a soft touch feeling (suede). It was difficult to impart a sense of

The present invention is intended to solve the above-mentioned drawbacks, and its purpose is to form a coating having a soft touch feel (suede-like) even on the surface of an article having an uneven or curved surface. The purpose of the present invention is to provide a covering sheet that can be used as a covering sheet.

[0007]

[Means for Solving the Problems] The covering sheet of the present invention mainly contains elastic beads and/or a porous inorganic material and at least one resin selected from the group consisting of acrylic resin, fluororesin, and silicone resin. It is formed from a resin composition contained as a component, thereby achieving the above object.

[0008] The present invention is characterized in that the elastic modulus and surface unevenness of the sheet are adjusted and performance is expressed by using an acrylic resin, a fluororesin, or a silicone resin, and elastic beads and/or a porous material. This invention relates to a covering sheet. Details of these are as follows.

The resin contained in the resin composition is at least one selected from the group consisting of acrylic resin, fluororesin, and silicone resin, and the glass transition point (Tg) of the resin used is -100 to 20. Preferably, the temperature is within the range of °C.

[0010] The above-mentioned acrylic resin includes a linear type and a crosslinked type, and either of them can be used. Examples of linear type acrylic resins include (meth)acrylic acid ester monomers such as ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl (meth)acrylate, α-methylstyrene, p - Styrene derivative monomers such as methylstyrene can be polymerized in a solution or the like in the presence of a peroxide or the like.

The weight average molecular weight of these acrylic resins is 2
A range of 0,000 to 1,000,000 is preferred. When the weight average molecular weight is less than 20,000, cracks are likely to occur in the sheet formed from the resin composition when it is spread. If the weight average molecular weight exceeds 1,000,000, it becomes difficult to dissolve in a solvent. For example, when creating a sheet by solvent casting, the viscosity of the solvent increases, so the resin can only be cast at a low concentration, and therefore the thickness Creating sheets of membrane would be costly.

[0012] When using a cross-linked acrylic resin, it is necessary to use a resin that has reactive groups such as hydroxyl groups or amino groups in advance, such as 2-hydroxyethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, etc. Using an acrylic resin containing (meth)acrylic acid ester, further,
For example, isocyanurates of hexamethylene diisocyanate, trimethylolpropane adducts, etc.
A melamine resin obtained by reacting formaldehyde with an isocyanate having a functional or higher functionality or a material with a polyfunctional amino group is added, and the coating sheet is made by reacting with heat during the production of the coating sheet (such as during solvent casting). It is preferable to create

[0013] In this case, it is preferable to add the above-mentioned material having two or more functional groups to the extent that the spreadability of the sheet (curve followability) is possible. The molecular weight of the acrylic resin at this time is selected from the viewpoint of the required spreadability of the sheet after crosslinking, but the weight average molecular weight is 1,000 to 1,000,000.
Preferably, the range is . By using such partially crosslinked acrylic, it is also possible to improve the solvent resistance of the coating sheet.

[0014] The above fluororesin, like acrylic resin,
There are linear types and cross-linked types, both of which can be used. Examples of fluororesins include ethylene, propylene and fluorinated ethylene such as difluorohydroxyethylene, aminodifluoroethylene, difluorodihydroxyethylene, aminotrifluoroethylene, hydroxytrifluoroethylene, carboxytrifluoroethylene, and chlorotrifluoroethylene. Polymers soluble in solvents such as alternating copolymers with and are preferably used.

The weight average molecular weight of the linear type fluororesin is preferably in the range of 20,000 to 1,000,000. When the weight average molecular weight is less than 20,000, cracks are likely to occur in the sheet when it is spread. If the weight average molecular weight exceeds 1,000,000, it becomes difficult to dissolve in a solvent. For example, when creating a sheet by solvent casting, the viscosity of the solvent increases, so the resin can only be cast at a low concentration, and therefore the thickness Creating sheets of membrane would be costly.

In addition, in the case of cross-linked fluororesins, the above-mentioned difunctional or higher functional isocyanate or melamine resin, which reacts with the above-mentioned reactive groups such as hydroxyl groups and amino groups, is usually added during the preparation of the coating sheet (solvent During casting, etc., the coating sheet is created by reacting with heat. in this case,
It is preferable to add the above-mentioned material having two or more functional groups to the extent that it is possible to spread the sheet (curve followability). The molecular weight of the fluororesin at this time is selected from the viewpoint of the required spreadability of the sheet after crosslinking, but the weight average molecular weight is 1,
A range of 000 to 1,000,000 is preferred. By using such a partially crosslinked fluororesin, it is also possible to improve the solvent resistance of the coating sheet.

[0017] The silicone resins mentioned above are of a linear type and a crosslinked type, and either of them can be used. When using a linear type silicone resin, there are two methods: one is to directly form a coating film by casting to create a covering sheet, and the other is to polymerize during casting film formation to create a covering sheet.

When a crosslinked silicone resin is used, it is usually formed into a sheet by the latter method.

These materials include, for example, dimethylpolysiloxane, diethylpolysiloxane, methylphenylpolysiloxane, which have a low glass transition temperature, and polydimethylsiloxaneoxy 1,4-, which has a high glass transition temperature.
These include blends of phenylene and the like, and materials having reactive groups such as hydroxyl groups at both ends of these materials. When directly forming a film by casting, these materials are polymerized in advance.

[0020] This silicone resin has a weight average molecular weight of 2
A range of 0,000 to 3,000,000 is preferred. When the polymerization average molecular weight is less than 20,000, cracks are likely to occur in the sheet when it is spread. Weight average molecular weight is 3,
If it exceeds 000,000, it becomes difficult to dissolve in a solvent.For example, when creating a sheet by solvent casting, the solvent viscosity becomes high, so the resin can only be cast at a low concentration, and a thick film sheet can be created. It will cost a lot of money to do so.

[0021] When polymerizing during casting, use a low-molecular silicone material or the above-mentioned polymeric material, and add a catalyst such as an acid, or add a bifunctional isocyanate or melamine resin during film formation. It polymerizes with heat to create a covering sheet.

Regarding the cross-linked type, a low-molecular silicone material or the above-mentioned polymeric material is used in the same manner as in the case of polymerization during casting, and in addition, at least trifunctional or higher functional isocyanate and melamine resin are added and heat applied during film formation. The material is polymerized to create a covering sheet.

[0023] This is because isocyanate and melamine resin are
Add as much as possible to spread the sheet (surface followability). By using partially crosslinked urethane in this way,
It is also possible to improve the solvent resistance of the coating sheet.

[0024] The elastic beads contained in the resin composition have the property of elastically recovering when released after being pressurized until their shape is deformed. , styrene resin, styrene-isoprene copolymer, etc. These elastic beads have a maximum particle size distribution of 1 to
It is preferable to add 20 to 400 parts of the resin having a diameter of 50 μm to 100 parts by weight (hereinafter referred to as parts) of the resin.

If the particle size of the elastic beads is less than 1 μm, it will be difficult to impart a sufficient soft touch feel (suede feel) to the obtained sheet, and if the amount added is too large than the above range, the sheet will become soft when stretched. Cracks are more likely to form on the surface. Further, the number of elastic beads is not limited to one type, and two or more types may be used in combination.

[0026] As the porous inorganic material contained in the resin composition, for example, hydrated silicic acid (SiO2.xH2
O) and hydrated aluminum silicate (Al2O39SiO2
・xH2O) and natural diatomaceous earth.

What is generally called white carbon is preferably used.

These inorganic materials vary depending on the thickness of the sheet to be obtained, but for example, when obtaining a sheet with a thickness of 100 μm or less, those with an average particle diameter of 30 μm or less are preferred, and more preferably 1 to 30 μm. It is 20 μm.

[0029] If the grain size is larger than 30 μm, the unevenness of the surface of the resulting coating becomes large, making it impossible to obtain an excellent soft feel, and cracks are likely to occur on the surface when the sheet is stretched.

[0030] In general, porous materials have oil absorption as one of the indicators of their degree of porosity. This varies depending on the properties of the binder used (type of resin, low molecular weight material), but for example, if the binder used has good compatibility with the above-mentioned inorganic material, a large amount of the binder will be retained in the inorganic material. The oil absorption amount of the material is 50ml/1
00g or more is preferable, more preferably 100-40g
It is 0ml/100g.

[0031] When the oil absorption amount is less than 50 ml/100 g, it is necessary to add a large amount of inorganic material to make the sheet surface rough (uneven surface), and as a result, the formed film becomes hard. Excellent soft feel cannot be obtained. The amount of the inorganic material added varies depending on the thickness of the sheet to be obtained and the compatibility between the inorganic material used and the binder. It is preferable to add 10 to 40 parts per 100 parts.

If the amount added is less than 10 parts, the coating surface cannot be sufficiently roughened, resulting in an excellent soft feel (slip feeling...
・Reduction in friction coefficient) cannot be obtained. If the amount added is more than 40 parts, cracks are likely to occur on the surface of the sheet during stretching. These inorganic materials are not limited to one type, and two or more types may be used in combination. Further, these inorganic materials and elastic beads may be used in combination.

[0033] Further, materials such as colorants such as pigments and dyes, and antioxidants are added to the resin composition as required. As the colorant, pigments and dyes used in paints can be used.

Examples of pigments include titanium oxide, iron oxide, carbon black, cyanine pigments, and quinacridone pigments. Dyes include azo dyes, anthraquinone dyes, indigoid dyes, and stilbenzene dyes.

Furthermore, metal powders such as aluminum flakes, nickel powders, gold powders, and silver powders may be used as the coloring agent. It is preferable that these materials have as fine particles as possible.

When using a highly opaque colorant, the amount of these additives is preferably in the range of 2 to 400 parts based on 100 parts of the solid content of the resin.

However, when these colorants are added, the soft touch feeling imparted by the elastic beads and inorganic materials may differ, so in systems with colorants added, the Tg of the resin, appropriate elastic beads, porous inorganic materials, etc. Ingredient quantities may vary.

Various functional agents may be added to impart various functions to the coated sheet of the present invention. Examples of the above-mentioned various functional materials include conductive materials, anti-condensation agents, photochromic compounds, and rust preventive agents.

[Form of Sheet] A resin composition is obtained by mixing and dispersing the above-mentioned materials. A soft touch layer (base layer) is created from the resin composition, and when the covering sheet is a single layer, this base layer serves as the covering sheet as it is.

The coating sheet of the present invention may consist of a single layer including only the base layer, or may consist of a plurality of layers. In the case of a single layer, printing (patterns) may be applied on one or both sides of the base layer using gravure printing, silk printing, offset printing, etc. to improve the design of the sheet. Furthermore, when the sheet is composed of multiple layers, there are, for example, the following forms.

(2) A sheet formed by laminating a colored layer containing a colorant on a transparent base layer (surface layer).

[0042] The colored layer is formed from the resin composition used for the base layer.

(2) A sheet formed by laminating a back layer on the base layer or the back side of the sheet in (2) above.

When the covering sheet is used for injection molding, stamping molding, etc., this back layer is used to increase adhesion to the molding resin and to withstand the shear stress of the molding resin.
Alternatively, it is provided to further improve the handling properties of the covering sheet.

[0045] The material forming the colored layer or back layer is preferably the same type of resin as the molding resin or a material with excellent compatibility in order to obtain adhesion with the molding resin (adhesion between the base layer or colored layer and the back layer). If the properties are poor, a primer layer may be provided between the two layers).

[0046] Furthermore, since the sheet is stretched as necessary and attached to the adherend, the layers to be laminated (colored layer and back layer) should be made of a material that is malleable at room temperature or at least under heating. preferable.

Examples of the resin used for the layer to be laminated (colored layer, back layer) include polystyrene, acrylic polymer, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, and ABS (acrylonitrile-butadiene-styrene copolymer). , modified polyphenylene oxide, polyphenylene sulfide, polyetherimide, polyetheretherketone, polyethylene sulfide, and the like.

■One side of the base layer or the sheets of ■ and ■ above (
In the case of sheets marked with ■ and ■, an adhesive layer is laminated on top of the laminated layers (i.e., on the back side of the base layer).

[0049] This adhesive layer is used so that the coating sheet can be easily attached to wallpaper, furniture, stationery, sanitary items, home appliances, automobile interiors, etc., or during molding such as extrusion molding or pultrusion molding. , or molding (
This is provided to improve the adhesion with the resin that will be molded later.

[0050] As the adhesive used for the adhesive layer, in order to easily attach the sheet, a pressure-sensitive adhesive,
Further, in order to improve the adhesion to the molding resin (immediately) after molding, a solvent type adhesive, a hot melt type adhesive, or a post-curing type adhesive is suitably used.

[0051] These adhesives may be used by mixing their respective materials in order to satisfy the performance. Furthermore, if good adhesion cannot be achieved with one type of adhesive depending on the materials of the sheet and the adherend, a plurality of different types of adhesive layers may be sequentially laminated.

[0052] Examples of the pressure-sensitive adhesives and solvent-based adhesives include rubber-based adhesives, acrylic-based adhesives, urethane-based adhesives, and silicone-based adhesives. Examples of hot melt adhesives include ethylene-vinyl acetate copolymer (EVA) and styrene-isoprene-styrene block copolymer (SIS). Post-curing adhesives include, for example, microcapsule adhesives. Examples of the material include uncrosslinked unsaturated polyester adhesives, uncrosslinked acrylic adhesives, and the like.

(2) A sheet comprising a protective layer laminated on the base layer or the surface of the sheet (1) to (3) above.

The protective layer is laminated to provide the sheet with shape retention during storage and use and surface protection after application.

[0055] Since the sheet is stretched as necessary and attached to the adherend, it is preferable that the protective layer is composed of a film (such as a thermoplastic resin film or a rubber film) that is malleable at room temperature or at least under heating. .

Examples of the thermoplastic resin include polyvinyl chloride, polyurethane, acrylic resin, polyester, ethylene-vinyl acetate copolymer, polyethylene, and polypropylene. Examples of rubber films include natural rubber, styrene-butadiene rubber,
Examples include nitrile-butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, urethane rubber, silicone rubber, and acrylic rubber.

A mixture of these thermoplastic resins and rubber can also be used. Alternatively, both films may be laminated.

These protective layers may be used as a protective layer until the adherend is used. By adding embossing or patterns to the surface of the protective layer, the surface shape (appearance) of the sheet can be changed after the protective layer is peeled off.

[0059] ■ A sheet in which a pattern such as printing is applied by the method described above to improve the design on the front or back surface of the base layer of the covering sheet described in Items (1) to (2) above.

[0060] The thickness of the curable sheet obtained in steps (1) to (3) above is 20 to
The thickness is preferably about 1,000 μm, and in the case of pasting on a flat surface, the thickness may be about 10 to 500 μm. Further, the thickness of other layers laminated on the sheet is usually 10 to 500 μm, and the thickness of the adhesive layer is particularly preferably 10 to 100 μm.

[Preparation of covering sheet] The covering sheet of the present invention may be prepared by any method. When the sheet is a single layer, the following casting method is preferred.

That is, the resin composition is sufficiently dissolved and dispersed in an organic solvent. The resulting solution is coated onto processing paper (usually polyethylene terephthalate film or paper with a silicone-treated surface) using equipment such as a knife coater, bar coater or reverse coater, and then dried to remove the solvent. to form a base layer.

A sheet is obtained by peeling the processing paper from the base layer. When the sheet is formed of multiple layers, it can be obtained by a casting method or a lamination method.

The casting method includes a method in which both the layer to be laminated and the base layer are cast, and a method in which only the base layer is laminated by casting.

In the former method, a solution containing the resin composition of one of the layers is coated on a processing paper, dried to remove the solvent to form a layer, and then the composition of the other layer is coated on top of this layer. Another layer is formed by coating a solution containing the substance and drying to remove the solvent.

The latter is produced by preparing sheets to be laminated in advance, then laminating the sheets by casting and drying to remove the solvent.

According to the lamination method, a resin composition for each layer is formed, and then both layers are laminated and pressed together using a (heated) roll press. At this time, an adhesive layer may be laminated between both layers to improve adhesion. The process paper used during manufacturing can be used as a protective sheet.

[How to use the covering sheet] The covering sheet of the present invention can be used in various ways.

In a method such as injection molding or stamping molding, in which a covering sheet is introduced into the mold in advance and affixed to the molded product at the same time as molding, the sheet is placed inside the mold at room temperature or by heating, and then vacuum and/or Or mold it tightly with pressure molding,
After that, normal molding is performed.

In methods such as extrusion molding and pultrusion, in which molded products are manufactured continuously, a covering sheet is introduced into the mold and attached to the surface of the molded product at the same time as the molded product is continuously molded, sizing, There are methods such as pasting it after cooling.

[0071] In the method of introducing the covering sheet into the mold, the covering sheet is rolled up in the front part of the mold. In the method of pasting the covering sheet immediately after molding, the covering sheet is pasted along the surface of the molded product using a pressure roller.

[0072] Vacuum (pressure) molding is carried out by a conventional method, with the covering sheet (base layer) of the present invention being laminated in advance on a sheet to be molded. When attaching the sheet to a long member such as wood or an aluminum sash, a commercially available profile laminator or the like can be used. At this time, it is preferable to provide the sheet with an adhesive layer in order to improve adhesion to the adherend.

[0073] The covering sheet laminated with pressure-sensitive adhesive is
Usually, it is pasted directly onto the surface of the molded product by hand or using a double vacuum forming machine (pasting machine) or the like.

[Applications of the covering sheet] The covering sheet of the present invention imparts a soft-touch feel to the surface of the product, so it can be used for parts that can be directly touched by people, or for parts that can be visually touched. It is not limited as long as it is a member that can be used.

For example, automotive interior parts include instrument panels, steering wheel gear lever knobs, doorknobs, armrests, various switches, seats, ceiling materials, etc. Housings for home appliances include portable products (telephones, cassette tape recorders, compact There are housings for office automation products such as personal computers, printers, keyboards, etc.

In addition, furniture products include chairs, desks, tables, wardrobes, etc., and architectural interior products include sanitary products such as sash frames, frame wood, various doors, wallpaper, etc.
Bathroom products include toilet seats, bathtubs, chairs, mats, shelves, etc. Sports equipment includes grips for bats, rackets, clubs, and defensive pads, and daily necessities and stationery products include various housings. , cases, containers, etc., as well as benches, chairs, stands, sofas, pillows, etc.

[0077]

[Action] A soft-touch (suede) feel can be easily imparted by simply pasting a sheet onto the surface of a molded product.
No painting space is required, and the working environment is not affected by solvents. Further, since the covering sheet of the present invention has excellent stretchability, it can be easily applied even in deep drawing by applying the sheet to an adherend while stretching the sheet. Since this sheet can be coated with a pattern such as printing at the same time, it is possible to impart design properties to the sheet.

[0078]

EXAMPLES The present invention will be explained in detail below based on examples.

(A) Preparation of coating sheet Example 1 Acrylic resin (copolymer of butyl acrylate and cyclohexyl acrylate, Mw=400,000, Tg=
-23℃, solid content 30%) 100 parts elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300
, acrylic-urethane elastic beads, average particle size 30 μm
) 150 parts and 2 parts of carbon black were mixed and dispersed with stirring.

[0080] This mixture was applied to an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., A106, film thickness 500 μm, hereinafter referred to as ABS sheet) and dried at 80° C. for 5 minutes to obtain a coating sheet. The thickness of the obtained covering sheet (thickness of the sheet other than ABS) was 100 μm.

Example 2 Acrylic resin (copolymer of butyl acrylate, 2-hydroxyethyl acrylate and hexadecyl acrylate, Mw=4,000, Tg=-30°C, OH value=5
, solid content 30%) 100 parts Elastic beads (manufactured by Sekisui Plastics Co., Ltd., SBX-6, cross-linked polystyrene elastic beads, average particle size 6 μm) 40 parts Isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd., Takenate D17)
0N, isocyanurate of hexamethylene diisocyanate, NCO=20.8%) (1:1 amount of OH group and NCO group of acrylic resin) were mixed and dispersed with stirring.

[0082] This mixture was treated with silicone to release the PE.
T-sheet (manufactured by Lintec Corporation, 3801, film thickness 38μ)
(hereinafter referred to as PET sheet) and heated at 80℃ for 15 minutes.
A covering sheet was obtained by drying for minutes. The thickness of the obtained covering sheet was 100 μm.

Thereafter, a stone pattern was printed by gravure printing, and a pressure-sensitive acrylic adhesive of 30 μm was laminated on the printed surface to prepare a covering sheet.

Example 3 Acrylic resin (styrene monomer, copolymer of butyl acrylate and hexyl acrylate, Mw=230.0
00, Tg = 15°C, solid content 35%) 100 parts elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS100
, acrylic-urethane elastic beads, average particle size 10 μm
) were mixed and dispersed with stirring.

This mixture was coated on a releasable PET sheet (manufactured by Lintec Corporation, 3801, film thickness 38 μm), and
A covering sheet was obtained by drying at 0° C. for 15 minutes. The thickness of the obtained covering sheet was 60 μm. After that, apply 30μm of SIS type hot melt adhesive.
were laminated to create a covering sheet.

Example 4 Fluorine resin (copolymer of ethylene and trifluoroethylene, Mw=40,000, Tg=-50°C, solid content 30%
) 100 parts elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., E
200 parts of BS300, acrylic-urethane elastic beads, average particle size 30 μm) were mixed and dispersed with stirring.

[0087] This mixture was coated on an ABS sheet with wood grain printing (manufactured by Sanpo Jushi Kogyo Co., Ltd., A106, wood grain was printed by gravure printing on a film thickness of 500 μm) and dried at 80° C. for 5 minutes to form a coating. I got a sheet for use. The thickness of the obtained covering sheet (thickness of sheets other than ABS) is 1
It was 00 μm.

Example 5 Fluorine resin (copolymer of ethylene and hydroxytrifluoroethylene, Mw=500,000, Tg=-45°C,
OH number = 455, solid content 30%) 100 parts elastic beads (Sekisui Plastics Co., Ltd., SBX-6, cross-linked polystyrene elastic beads, average particle size 6 μm) 40 parts carbon black 3 parts isocyanate (Takeda Pharmaceutical Co., Ltd.) Co., Ltd., Takenate D
170N, isocyanurate of hexamethylene diisocyanate, NCO=20.8%) (1:0.05 ratio of OH group to NCO group of acrylic resin) were mixed and dispersed with stirring.

This mixture was printed on a PVC sheet (manufactured by Tsutsunaka Plastic Co., Ltd., Kydac, film thickness 3 mm).
(printed with wood grain using gravure printing) and heated at 80℃ for 3
A covering sheet was obtained by drying for 0 minutes. Thickness of the obtained covering sheet (thickness of sheets other than ABS)
was 100 μm.

Example 6 Silicone resin (methylphenyl polysiloxane (Mw
= 100,000) and polydimethylsiloxaneoxy 1
, 4-phenylene (Mw = 200,000), Tg = -40°C, solid content 30%) 100 parts elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300
, acrylic-urethane elastic beads, average particle size 30 μm
) 200 parts and 4 parts of carbon black were mixed and dispersed with stirring.

[0091] This mixture was applied to an ABS sheet with wood grain printing (manufactured by Sanpo Jushi Kogyo Co., Ltd., A106, wood grain was printed by gravure printing on a film thickness of 500 μm) and dried at 80° C. for 5 minutes to form a coating. I got a sheet for use. The thickness of the obtained covering sheet (thickness of sheets other than ABS) is 1
It was 00 μm.

Example 7 Silicone resin (methylphenyl polysiloxane (Mw
= 100,000) and polydimethylsiloxaneoxy 1
, 4-phenylene (Mw=200,000), dimethylpolysiloxane having hydroxyl groups at both ends (Mw=3,0
00) blend, Tg = -80°C, OH value = 2, solid content 30%) 100 parts elastic beads (manufactured by Sekisui Plastics Co., Ltd.,
SBX-6, elastic beads of cross-linked polystyrene, average particle size 6 μm) 40 parts Isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd., Takenate D170N, isocyanurate of hexamethylene diisocyanate, NCO = 20.8%) 1.8
(1:1 ratio of OH group to NCO group of silicone resin) 15 parts of quinacridone red were mixed and dispersed with stirring.

This mixture was coated on mold release PET (3801, manufactured by Lintec Corporation, film thickness 38 μm) and heated at 80°C for 1
A covering sheet was obtained by drying for 5 minutes. The thickness of the obtained covering sheet was 60 μm. Thereafter, a 30 μm thick pressure-sensitive silicone adhesive was laminated to prepare a covering sheet.

Example 8 Acrylic resin (copolymer of butyl acrylate and cyclohexyl acrylate, Mw=400,000, Tg=
-23℃, solid content 30%) 100 parts Porous inorganic material (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 620, average particle size 12 μm, oil absorption 180 ml/1
00g) 30 parts and 2 parts of carbon black were mixed and dispersed with stirring.

[0095] This mixture was coated on an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., A106, film thickness 500 μm).
A covering sheet was obtained by drying at °C for 5 minutes. The thickness of the obtained covering sheet (thickness of the sheet other than ABS) was 80 μm.

Example 9 Acrylic resin (copolymer of butyl acrylate, 2-hydroxyethyl acrylate and hexadecyl acrylate, Mw=4,000, Tg=-30°C, OH value=5
, solid content 30%) 100 parts porous inorganic material (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 72, average particle size 2.5 μm, oil absorption 220 ml/1
1.8
(1:1 ratio of OH groups and NCO groups of silicone resin) were mixed and dispersed with stirring.

[0097] This mixture was coated on a release PET sheet (manufactured by Lintec Corporation, 3801) and dried at 80°C for 15 minutes to obtain a coating sheet. The thickness of the obtained covering sheet was 100 μm. After that, S.I.
A covering sheet was prepared by laminating S-type hot melt adhesive with a thickness of 30 μm.

Example 10 Acrylic resin (methyl methacrylate, copolymer of butyl acrylate and hexyl acrylate, Mw=23
0,000, solid content 35%) 100 parts Porous inorganic material (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 72, average particle size 2.5 μm, oil absorption 310 ml/1
00g) 20 parts titanium oxide 20 parts
1) and dried at 80° C. for 15 minutes to obtain a covering sheet. The thickness of the obtained covering sheet was 150 μm.

Example 11 Fluorine resin (alternating copolymer of ethylene and trifluoroethylene, Mw=40,000, Tg=-50°C, solid content 3
0%) 100 parts Porous inorganic material (Fuji Davison Chemical (
20 parts of Cyroid 72 (manufactured by Co., Ltd., average particle size 2.5 μm, oil absorption 220 ml/100 g) were mixed and dispersed with stirring.

[0100] This mixture was coated on an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., Ai06, film thickness 500 μm), and
A covering sheet was obtained by drying at 0° C. for 20 minutes. The thickness of the obtained covering sheet was 100 μm.

Example 12 Fluorine resin (copolymer of ethylene and hydroxytrifluoroethylene, Mw=500,000, Tg=-45°C,
OH number = 455, solid content 30%) 100 parts Porous inorganic material (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 244, average particle size 1.8 μm, oil absorption 310 ml/
100g) 20 parts isocyanate (Takeda Pharmaceutical Co., Ltd.)
Takenate D170N, isocyanurate of hexamethylene diisocyanate, NCO = 20.8%)8.
2 parts (fluororesin's OH group and NCO group are 1:0.05)
20 parts of iron chloride were mixed and dispersed with stirring.

[0102] This mixture was applied to a mold release PET (3801 manufactured by Lintec Corporation) and dried at 80°C for 15 minutes to obtain a coating sheet. The thickness of the obtained covering sheet was 100 μm.

[0103] After that, apply 30 μm of pressure-sensitive silicone adhesive.
A covering sheet was prepared by laminating the sheets.

Example 13 Silicone resin (methylphenyl polysiloxane (Mw
= 100,000) and polydimethylsiloxaneoxy 1
, 4-phenylene (Mw = 200,000), Tg = -40°C, solid content 30%) 100 parts Porous inorganic material (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 620, average particle size 12 μm, oil absorption 180ml/1
00g) 30 parts and 4 parts of carbon black were mixed and dispersed with stirring.

[0105] This mixture was coated on an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., A106, film thickness 500 μm).
A covering sheet was obtained by drying at °C for 5 minutes. The thickness of the obtained covering sheet (thickness of the sheet other than ABS) was 100 μm.

Example 14 Silicone resin (methylphenylpolysiloxane (Mw
= 100,000) and polydimethylsiloxaneoxy 1
, 4-phenylene (Mw=200,000), dimethylpolysiloxane having hydroxyl groups at both ends (Mw=3,0
00) blend, Tg = -80°C, OH value = 2, solid content 30%) 100 parts porous inorganic material (manufactured by Fuji Davison Chemical Co., Ltd., Cyroid 244, average particle size 1.8 μm,
Oil absorption 310ml/100g) 30 parts isocyanate (
Manufactured by Takeda Pharmaceutical Co., Ltd., Takenate D170N, isocyanurate of hexamethylene diisocyanate, NCO
= 20.8%) 1.8 parts (OH group of silicone resin and N
and CO groups) were mixed and dispersed with stirring.

[0107] This mixture was coated on mold release PET (3801, manufactured by Lintec Corporation) and dried at 80°C for 15 minutes to obtain a coating sheet. The thickness of the obtained covering sheet was 100 μm.

Thereafter, a stone pattern was printed by gravure printing, and a pressure-sensitive acrylic adhesive of 30 μm was laminated on the printed surface to prepare a covering sheet.

Example 15 Acrylic resin (copolymer of methyl methacrylate, butyl acrylate and heptyl acrylate, Mw=4
60,000, Tg=10°C, solid content 30%) 100 parts elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS100
, acrylic-urethane elastic beads, average particle size 10 μm
) 80 parts and 4 parts or more of carbon black were mixed with stirring.

[0110] This mixture was coated on an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., A106, film thickness 500 μm).
A covering sheet was obtained by drying at °C for 5 minutes. The thickness of the obtained covering sheet (thickness of the sheet other than ABS) was 100 μm.

Example 16 Silicone resin (dimethylpolysiloxane, Mw=2,
000,000, Tg=-127℃, solid content 30%)1
00 parts elastic beads (manufactured by Sekisui Plastics Co., Ltd., EAX-20
Crosslinked polyacrylic acid ester elastic beads, average particle size 2
0 μm) 80 parts and 50 parts or more of titanium oxide were mixed with stirring.

[0112] This mixture was coated on a mold release PET (manufactured by Lintec Corporation, 3801, film thickness 38 μm) and heated at 80°C for 1
A covering sheet was obtained by drying for 5 minutes. The thickness of the obtained covering sheet was 100 μm.

[0113] This mixture was coated on an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., A106, film thickness 500 μm).
A covering sheet was obtained by drying at °C for 5 minutes. The thickness of the obtained covering sheet (thickness of the sheet other than ABS) was 100 μm. Thereafter, a 30 μm thick pressure-sensitive acrylic adhesive was laminated to form a covering sheet.

Example 17 Acrylic resin (copolymer of butyl methacrylate and butyl acrylate, Mw=360,000, Tg=0
℃, solid content 30%) 100 parts porous inorganic material (manufactured by Fuji Davison Chemical Co., Ltd., Cyroid 244, average particle size 1.8 μm, oil absorption 310 ml/
100g) 20 parts and 4 parts or more of carbon black were mixed with stirring.

[0115] This mixture was coated on an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., A106, film thickness 500 μm).
A covering sheet was obtained by drying at °C for 5 minutes. The thickness of the obtained covering sheet (thickness of the sheet other than ABS) was 100 μm.

Example 18 Silicone resin (dimethylpolysiloxane, Tg=-1
27°C, solid content 30%) 100 parts porous inorganic material (manufactured by Fuji Davison Chemical Co., Ltd., Cyroid 244, average particle size 1.8 μm, oil absorption 310 ml/100 g) 40 parts carbon black or more with stirring Mixed.

[0117] This mixture was coated on a mold release PET (manufactured by Lintec Corporation, 3801, film thickness 38 μm) and heated at 80°C for 1
A covering sheet was obtained by drying for 5 minutes. The thickness of the obtained covering sheet was 100 μm. Thereafter, a 30 μm thick pressure-sensitive acrylic adhesive was laminated to form a covering sheet.

(B) Evaluation of curable sheets As shown in Tables 1 and 2, the adhesion of the coating sheets obtained in each of the above Examples to the adherend and the soft appearance (feel) after the sheets were cured.
and the appearance was evaluated.

[0119] Adhesion was determined by an adhesion test using a grid test (
The number of grid points remaining after the tape was peeled off), and the soft appearance (sensation) and appearance were visually observed. The results are also shown in Tables 1 and 2. The details of each test method in each example are as follows.

[0120] Method for attaching a sheet to the surface of a molded product at the same time as injection molding: ABS resin (manufactured by Denki Kagaku Kogyo Co., Ltd., ABS-ME) is used as the resin for injection molding, and this resin is heated from the injection machine 15 into a metal. The sheet placed inside the mold was attached by injection into the mold.

[0121] Method of attaching the sheet by hand: A steel plate curved into a convex lens shape (radius of curvature 50 cm, diameter of the lower surface 30 cm) was used as the adherend, and the sheet was attached onto this convex surface.

[0122] Method of attaching a sheet to the surface of a molded product at the same time as extrusion molding: Polystyrene (HT-516, manufactured by Mitsubishi Monsanto Chemical Co., Ltd.) is used as the resin for extrusion molding, and the molded product is extruded from a mold. A sheet was attached to the surface of the product using a laminator.

[0123] Attaching method by stamping: The molding resin is ABS resin (manufactured by Denki Kagaku Kogyo Co., Ltd., ABS-M).
Using E), this resin was introduced in the form of a lump from an extruder into a mold and pressed, and a sheet placed in the mold was pasted and molded.

Vacuum forming: The sheet was heated to a predetermined temperature and was attached to the surface of a hemispherical ABS molded product using a vacuum forming machine.

[0125] Pasting method using SMC: The molding resin is
Polyester-based SMC (manufactured by Takeda Pharmaceutical Co., Ltd.) was used, and this SMC was introduced into a mold by hand, pressed, and the sheet placed in the mold was pasted and molded.

[0126] Method of attaching a sheet to the surface of a molded product at the same time as pultrusion molding: Polystyrene (HT-516, manufactured by Mitsubishi Monsanto Chemical Co., Ltd.) is used as the molding resin, and the long member is molded while being pulled out from the mold. A sheet was attached to the surface of the product.

Method for pasting sheets using a laminator: A covering sheet and an aluminum plate (2 mm thick) were put into two pressure rolls at the same time and pressure bonded.

(Comparative Example) Comparative Example 1 ABS resin sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., A205,
Soft touch paint (Cashew Co., Ltd.) on film thickness 500μm
Co., Ltd., Cenosoft II) was coated to a coating thickness of 50 μm and cured by heating at 80° C. for 30 minutes.

[0129] Using the obtained sheet, an injection molding test was conducted in the same manner as in Example 1. As a result, due to insufficient elongation of the sheet, the sheet could not be molded into the shape of the mold, and cracks appeared in the sheet when the resin was injected.

[0130]

[Table 1]

[0131]

[Table 2]

[0132]

Effects of the Invention The coating sheet of the present invention has excellent stretchability before molding, so it can be applied not only to flat articles but also to the surface of articles with uneven or curved surfaces, and when cured, it can be applied to A coating having a soft touch feel (suede-like) with excellent solvent resistance and scratch resistance can be formed on the surface of an article. Therefore, it has the advantage of eliminating the conventional painting space problems and environmental problems such as solvents, and also makes it easy and inexpensive to decorate various plastic molded objects and metal molded objects such as housings for OA equipment, home appliances, stationery, etc. It has the advantage of being able to

Claims (1)

[Claims] [Claim 1] A resin composition containing as main components elastic beads and/or a porous inorganic material and at least one resin selected from the group consisting of acrylic resin, fluororesin, and silicone resin. A covering sheet.