JP4863033B2 - Method for producing thermosetting resin decorative material - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention belongs to the technical field of house interior materials, and particularly relates to a thermosetting resin decorative material suitably used for kitchen door surface materials, kitchen back panels, bathroom wall materials, floor materials and the like.
[0002]
[Prior art]
This type of thermosetting resin decorative material is manufactured by hot press molding. That is, a decorative sheet is prepared by laminating a biaxially stretched polyethylene terephthalate (PET) sheet printed with a pattern layer and a non-woven fabric with the pattern layer sandwiched therebetween, and the decorative sheet is placed on the SMC ( It is manufactured by integrally molding with a sheet molding compound (see, for example, Japanese Patent Application Laid-Open Nos. 7-60911 and 8-118384).
[0003]
[Problems to be solved by the invention]
As described above, the thermosetting resin decorative material is manufactured by a press molding machine, but the curing temperature of SMC is generally as high as around 150 ° C., and when the mold is heated to about 150 ° C. and molded, In the biaxially stretched PET, since it softens and causes heat shrinkage, there are problems such as the surface becoming wrinkled skin or wrinkles.
[0004]
In addition, when uncured fiber reinforced thermosetting resin (FRP) such as SMC is cured while being molded by hot press molding, in addition to the heat directly applied from the press molding machine, the interior when SMC is further cured Due to the heat generation, there is a problem that the molding resin generates heat above the mold temperature, and the decorative sheet is wrinkled or thermally discolored due to heat shrinkage.
[0005]
The present invention has been made in view of the above-described problems, and the object of the present invention is a method for producing a thermosetting resin cosmetic material that does not cause surface appearance defects such as cocoon skin, wrinkles, and discoloration. Is to provide.
[0006]
[Means for Solving the Problems]
To achieve the above object, a manufacturing method of a thermosetting resin decorative material according to the present invention, 1 50 when ℃ was heated in an atmosphere for 30 minutes thermal shrinkage transparent thermoplastic resin sheet of 1% or less A decorative sheet with a fiber sheet laminated on one side is prepared, and a fiber-reinforced thermosetting resin base material and a fiber-reinforced thermosetting resin base material are placed between a pair of molds of a press molding machine. Placed facing the fibrous sheet side of the sheet, press-molded at a molding temperature set to be 20 ° or more lower than the thermal deformation temperature of the thermoplastic resin sheet, and fiber reinforced thermosetting the decorative sheet is integrally laminated to the surface of the resin base material is characterized in Rukoto.
[0007]
Then, in the process for producing a thermosetting resin decorative material having the above structure, it can have use a decorative sheet concealing layer is provided fibrous sheet side of the thermoplastic resin sheet. Moreover, you may make it form an uneven | corrugated pattern on the opposite side to the fibrous sheet of a thermoplastic resin sheet with an embossing plate at the time of shaping | molding .
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Figure 1 is an illustration of a decorative sheet used in the method for producing a thermosetting resin decorative material according to the present invention. A decorative sheet 10 in FIG. 1 (A) is obtained by laminating a fibrous sheet 12 on one side of a transparent thermoplastic resin sheet 11, and the decorative sheet 10 in FIG. 1 (B) is a transparent thermoplastic resin sheet 11. A fibrous sheet 12 is laminated on one side with an adhesive layer 13 interposed therebetween, and the decorative sheet 10 in FIG. 1 (C) has a decorative layer 14 laminated on one side of a transparent thermoplastic resin sheet 11. 1 to (D), the decorative sheet 10 of FIG. 1 (D) has a decorative layer 14 laminated on one side of a transparent thermoplastic resin sheet 11, and from above. The fibrous sheet 12 is directly laminated. Note that the decorative sheet used in the present invention is not limited to the one shown in FIG. 1 and may have other configurations.
[0009]
Figure 2 is a sectional view schematically showing an example of a thermosetting resin decorative material which is more produced in the present invention, the thermosetting resin decorative material, the type of the decorative sheet 10 shown in FIG. 1 (C) Is laminated on the surface of the fiber reinforced thermosetting resin substrate 20.
[0010]
The thermosetting resin decorative material D shown in FIG. 2 is manufactured by molding the fiber-reinforced thermosetting resin base material 20 and simultaneously laminating and integrating the decorative sheet 10 on the surface thereof. Conventionally, when manufacturing a decorative material having such a configuration, appearance defects such as cocoon skin and wrinkles have sometimes occurred on the surface. When this inventor researched, it turned out that it is a cause that the thermoplastic resin sheet 11 of the decorative sheet 10 heat-shrinks at the time of a hot press. Therefore, the thermoplastic resin sheet 11 constituting the decorative sheet 10 is selected as low as possible in the thermal contraction rate. As a result of examination based on experiments, the heat shrinkage rate was evaluated in accordance with the measurement method of “JISC 2318” but extended only to the heating time to 30 minutes (however, the flow direction during sheet film formation (MD)) It has been found that a thermoplastic resin sheet having a value of 1% or less may be used with a larger value among the values of the width direction (TD) and the value in the width direction (TD).
[0011]
Examples of such a thermoplastic resin sheet include polyethylene naphthalate (PEN), polybutylene naphthalate, or low heat-shrinkable polyethylene terephthalate (PET) that has been heat-treated so that the heat shrinkage rate is 1% or less. Biaxially stretched polyethylene naphthalate is preferable in consideration of heat resistance, transparency, contamination, chemical properties, etc. in addition to low heat shrinkage. And the thickness of the thermoplastic resin sheet to be used is 25-200 micrometers, Preferably it is 50-100 micrometers. Moreover, you may use the thermoplastic resin sheet colored as needed. If necessary, on the entire surface of the thermoplastic resin sheet, a number of small holes with a diameter of about 0.1 to 1 mm that are not visually noticeable are formed, and the decorative sheet and the fiber reinforced thermosetting resin substrate are heated and pressurized. When molding, air remaining between the two may be easily removed.
[0012]
As the fibrous sheet, non-woven fabrics, woven fabrics, knitted fabrics, and the like that can be selected from olefin resins such as polyethylene, polypropylene, and ionomer, acrylic resins, and polyester resins can be used. Among these, polyester resins are preferable in consideration of heat resistance, cost, strength, and the like. Furthermore, organic polymer fibers such as PEN, nylon, and aramid resin, or inorganic fibers such as glass, carbon (graphite, etc.), silica, and potassium titanate can be used. The basis weight of the fiber sheet to be used is about 10 to 400 g / m ² , and the thickness of the fiber is about 30 to 250 denier (D). Moreover, the fiber sheet colored as needed is used.
[0013]
The thermoplastic resin sheet or the fibrous sheet may be subjected to a decoration treatment to give a desired design appearance as necessary. As a decoration process, a colorant (selected from among those exemplified as an ink colorant as described below) is kneaded into either one of the thermoplastic resin sheet or the fiber sheet or both sheets themselves. , A form in which a decorative layer such as a pattern ink layer or a metal thin film layer is formed on one or both of the two sheets, a form in which both the kneading of the colorant and the formation of the decorative layer are used together, or thermoplasticity There exists a form etc. which form an uneven | corrugated pattern in the surface (opposite side with a fiber sheet) of a resin sheet.
[0014]
When a pattern ink layer is formed as a decoration layer, it may be printed on the side (back side) of the thermoplastic resin sheet in contact with the adhesive layer, or on the opposite side (front side) or both sides of the adhesive layer. Good. Alternatively, two layers of the same or different thermoplastic resin sheets may be laminated and bonded to each other, and a pattern ink layer may be formed between both sheets (the back side of the upper sheet or the front side of the lower sheet). The printing method may be gravure, offset, silk screen, ink jet, etc. Also, the pattern ink to be used is a binder resin, pigments, dyes and other colorants, and if necessary, antioxidants, surfactants, stabilizers, constitutions Uses other additives such as pigments and plasticizers.
[0015]
As binder resin, cellulose acetate, cellulose acetate propionate, fiber resin such as nitrified cotton, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethyl hexyl (meth) acrylate, (Meth) acrylic acid methyl methacrylate- (meth) acrylic acid butyl copolymer, (meth) acrylic acid methyl-styrene copolymer and other (meth) acrylic acid ester homopolymer or acrylic resin, vinyl chloride-acetic acid One type or a mixture of two or more types of vinyl copolymers, two-component curable urethane resins, polyester resins, polyamide resins and the like are used.
[0016]
Examples of pigments include petals, chrome vermilion, yellow lead, titanium yellow, cobalt blue, ultramarine, titanium white, niantimony trioxide, carbon black, iron black and other inorganic pigments, brass, aluminum, titanium dioxide coated mica, etc. Bright pigments made of scale-like foil pieces, organic pigments (or paints) such as quinacridone red, polyazo red, isoindolinone yellow, benzidi yellow, phthalocyanine blue, and indanthrene blue are used.
[0017]
In addition, the pattern to be printed is a pattern such as a wood grain pattern, a stone pattern, a grain pattern, a crest pattern, a cloth pattern, a tiled pattern, a brickwork pattern, a geometric pattern, characters, symbols, a solid pattern alone, or A combination of two or more of these is used.
[0018]
The metal thin film layer as the decoration layer includes a metal thin film layer made of gold, silver, chromium, aluminum or the like formed by vacuum deposition, sputtering, or the like.
[0019]
In order to prevent the texture and texture of the fiber sheet from affecting the appearance design, a concealing layer is provided on the fiber sheet side of the thermoplastic resin sheet, and the texture and texture of the fiber sheet are visually observed. It is good to hide so that it cannot. However, when the textile sheet texture or texture appearance of the fiber sheet is utilized as a design, of course, the concealing layer is not provided. The concealing layer is a solid printing (coating) layer using an ink obtained by adding a concealing pigment such as titanium white, carbon black, or luster pigment in the resin binder as described above, or a metal thin film such as aluminum or chromium. Use to form. When the thermoplastic resin sheet is subjected to a decoration treatment, a concealing layer is provided on the fibrous sheet side with respect to the layer having the decoration treatment. Alternatively, the entire solid layer or the metal thin film as the decorative layer as described above can also be used as the concealing layer.
[0020]
In addition, examples of the concavo-convex pattern include a wood grain conduit groove, a grain texture, a pear texture, a granite cleavage surface, a tiled or brick joint texture groove, a crest, a fabric texture, a hairline, and the like. As a method for forming a concavo-convex pattern, when a fiber reinforced thermosetting resin substrate and a decorative sheet are laminated and molded, an embossed plate having a reverse concavo-convex pattern of a desired concavo-convex pattern is placed on the surface of the decorative sheet. In this state, it is preferable to insert the mold into a mold, heat and press to mold, and after the molding is completed, open the mold and release the embossed plate. Usually, as will be described later (see FIG. 3), the mold on the side contacting the decorative sheet is also used as the embossed plate.
[0021]
As an adhesive for bonding the thermoplastic resin sheet and the fibrous sheet, a two-component curable urethane resin is preferably used. Specifically, acrylic polyols, polyester polyols, polyether polyols, polycarbonate polyols and other polyols are the main ingredients, and aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate and naphthalene diisocyanate, or 1,6-hexamethylene. It is an adhesive having an aliphatic or alicyclic isocyanate such as diisocyanate, isophorone diisocyanate, and hydrogenated tolylene diisocyanate as a curing agent. In addition, other thermosetting resins such as epoxy resins and melamine resins, thermoplastic resins such as acrylic resins, polyolefin resins, polyvinyl acetate, thermoplastic urethane resins, and polyamide resins can also be used. The coating amount of the adhesive layer, and 10 to 100 g / m ² approximately. In addition, high concealment pigments such as bright pigments made of titanium white, carbon black, and aluminum foil pieces are added as necessary to conceal the texture of woven fabrics, knitted fabrics, or the formation of nonwoven fabrics. May be.
[0022]
When laminating both a thermoplastic resin sheet and a fibrous sheet using a thermosetting resin adhesive, heat the uncured adhesive by a known coating method such as roll coating, gravure roll coating, comma coating, etc. Apply a predetermined amount to the plastic resin sheet side or fiber sheet side, and if there is a dilution solvent, dry it off and then superpose both sheets with an adhesive layer between them to react the adhesive. A method of curing and bonding the two sheets together (so-called dry laminating method) is common.
[0023]
In addition, when laminating both thermoplastic resin sheet and fibrous sheet using thermoplastic resin adhesive, either heat-melt adhesive is applied by extrusion from T-die, A method is generally employed in which a predetermined amount is applied to one side, and then both sheets are overlapped with an adhesive layer therebetween, and the adhesive is cooled and solidified to laminate the two sheets (so-called extrusion laminating method). .
[0024]
In addition, even if there is no adhesive layer, if it has thermal adhesiveness (fusion) between the thermoplastic resin sheet and the fibrous sheet, or between the decorative layer and the fibrous sheet, the adhesive layer is omitted, Both sheets are directly heated and pressed to bond them (a configuration as shown in FIG. 1A or FIG. 1D).
[0025]
The fiber reinforced thermosetting resin is composed of a composite of a thermosetting resin such as an unsaturated polyester resin, an epoxy resin, a diallyl phthalate resin, a melamine resin, or a phenol resin and a reinforcing fiber. The reinforcing fiber is selected from those similar to those exemplified as the fibrous sheet.
[0026]
The most common fiber-reinforced thermosetting resin is one using an unsaturated polyester resin as the thermosetting resin and glass fiber as the reinforcing fiber. As the shape of the fiber reinforced thermosetting resin substrate, a flat plate, a curved plate, or various three-dimensional shapes are used.
[0027]
In order to form a fiber-reinforced thermosetting resin substrate into a desired shape, an uncured or semi-cured product of fiber-reinforced thermosetting resin is inserted between a pair of male and female molds, and the uncured material is heated and pressed. The product or semi-cured product (the thermosetting resin component therein) is reacted to be cured.
[0028]
As the uncured or semi-cured product of the fiber reinforced thermosetting resin, those having a known form such as SMC (sheet molding compound), BMC (bulk molding compound), prepreg and the like are used. A fiber reinforced thermosetting resin (FRP) is obtained by curing these SMC, BMC, prepreg and the like (the thermosetting resin therein). The molding conditions for reacting and curing these uncured or semi-cured products to form a fiber reinforced thermosetting resin are generally molding temperature (mold temperature): about 100 to 160 ° C., molding pressure: 20 ˜100 kg / cm ² and molding time: about 5 to 20 minutes.
[0029]
However, the object of the present invention is to ensure the effect of preventing the rust skin and wrinkles of the decorative sheet at the time of molding, as well as exudation of additives and low molecular weight components from the thermoplastic resin sheet (bleed), heat to prevent discoloration, to set so that the molding temperature is a low temperature 20 ° C. or higher than the thermal deformation temperature of the thermoplastic resin sheet.
[0030]
FIG. 3 is an explanatory view showing a typical method for producing a thermosetting resin decorative material, which will be described next.
[0031]
First, the SMC 40 (or other uncured or cured product of fiber reinforced thermosetting resin) and the decorative sheet 10 are inserted between the pair of molds 31 and 32 of the press molding machine 30. At this time, the front side of the decorative sheet 10 (the side that becomes the outer surface when it becomes a decorative material, that is, the side of the thermoplastic resin sheet 11) is directed toward the mold 31 for forming the outer surface of the decorative material. Place. Then, the SMC 40 is placed so as to face the back surface side (the fiber sheet 12 side) of the decorative sheet 10. This is the state of FIG. In this press molding machine 30, in order to form a concavo-convex pattern on the surface of the decorative material to be molded, a reverse concavo-convex pattern 31 a having a desired concavo-convex pattern is formed on the surface of the mold 31 that contacts the surface side of the decorative sheet 10. is there.
[0032]
Next, the rams 33 and 34 of the fluid pressure cylinder that supports the dies 31 and 32 are driven forward, and a predetermined molding pressure is applied to the decorative sheet 10 and the SMC 40. The molds 31 and 32 are heated to a predetermined molding temperature by means of heated steam, an electric heater, induction heating or the like. And when predetermined molding time passes, after cooling type | molds 31 and 32 by flowing cooling water etc., the type | molds 31 and 32 are open | released and the fiber reinforced thermosetting resin base | substrate with which the decorative sheet 10 was laminated | stacked integrally on the surface. A decorative material D made of the material 20 is obtained. Here, if the surface of the mold 31 is a mirror surface, a decorative material D (FIG. 2) having a mirror surface is obtained. However, in the case of the illustrated press molding machine 30, the uneven surface 11a is applied to the surface of the decorative material at the time of molding. And a thermosetting resin decorative material D as shown in FIG. 4 is obtained.
[0033]
The use of the thermosetting resin decorative material obtained in the present invention includes interior materials such as house floors, walls and ceilings, interior materials such as bathroom floors, walls and ceilings, bathtubs, washstands, kitchen doors and kitchens. Examples include back panels, cabinets for home appliances, containers, vehicle interior materials, desks, furniture such as bags.
[0034]
【Example】
(Example)
The thickness is 100 μm, and the thermal shrinkage rate during heating for 30 minutes in a 150 ° C. atmosphere is 0.9% (however, the flow direction (MD) during sheet film formation is 0.9%, and the width direction (TD) is 0) Prepared a thermoplastic resin sheet (manufactured by Teijin DuPont) made of transparent biaxially stretched polyethylene naphthalate (PEN) with a maximum value of 0.9%. Ink adhesion was improved by applying a discharge treatment.
[0035]
Next, a two-component curable urethane resin obtained by adding 8 parts by mass of 1,6-hexamethylene diisocyanate to 100 parts by mass of polyester polyol as a binder resin is used for the corona discharge treatment surface of the thermoplastic resin sheet, and titanium is used for this. A marble pattern was gravure-printed with an ink to which a pigment composed of white, petal, phthalocyanine blue and chrome-lead was added, to form a decorative layer composed of a pattern ink layer.
[0036]
Next, a polyester nonwoven fabric having a thickness of 60 μm was used as a fibrous sheet, and the fibrous sheet was dry laminated on the thermoplastic resin sheet to obtain a decorative sheet. Specifically, an adhesive layer of a two-component curable urethane resin obtained by adding 8 parts by mass of 1,6-hexamethylene diisocyanate to 100 parts by mass of polyester polyol is formed in an amount of 12 g / m ² and dry-laminated. It laminated | stacked by making it age at 40 degreeC for 3 days.
[0037]
SMC (Takeda Pharmaceutical Co., Ltd.) using a press molding machine having a pair of male and female dies plated with chromium on the surface, using the above decorative sheet, unsaturated polyester resin as thermosetting resin, and glass fiber as reinforcing fiber Is set in the mold so that the fiber sheet of the decorative sheet and the SMC face each other, and is heated for 2 minutes at a mold temperature of 140 ° C. and a pressure of 50 kg / cm ² for thermosetting as a molded product. A functional resin decorative material was obtained. The surface of the resulting thermosetting resin decorative material was extremely excellent in mirror surface, and no cocoon skin or wrinkles on the surface was observed visually.
[0038]
(Comparative example)
It has a thickness of 100 μm and a thermal shrinkage rate of 2.2% when heated in an atmosphere at 150 ° C. for 30 minutes (however, the flow direction (MD) during film formation is 2.2% and the width direction (TD) is 0) Prepare a thermoplastic resin sheet (manufactured by Teijin DuPont) made of transparent polyethylene terephthalate (PET) with a maximum value of 2.2%, and apply corona discharge treatment to the back side. Improved the ink adhesion. Hereinafter, a decorative sheet was obtained in the same manner as in the above example.
[0039]
And when it integrally molded with the press molding machine similarly to the Example and the thermosetting resin cosmetic material as a molded article was obtained, the cloudy cocoon skin generate | occur | produced on the surface, and the mirror surface was not obtained. In addition, wrinkles due to the flow of the molding resin also occurred at the end of the molded product.
[0040]
【Effect of the invention】
The method for producing a thermosetting resin decorative material according to the present invention includes a thermoplastic resin sheet having a thermal shrinkage of 1% or less when heated in a 150 ° C. atmosphere for 30 minutes as a thermoplastic resin sheet constituting the decorative sheet. Since it has been selected, even if heat and pressure during hot press molding of the fiber reinforced thermosetting resin are applied, appearance defects on the surface of the decorative material such as cocoon skin and wrinkles due to heat shrinkage do not occur. Moreover, the decorative sheet is laminated and integrated on the surface of the fiber-reinforced thermosetting resin substrate by press molding at a molding temperature set to be 20 ° or more lower than the thermal deformation temperature of the thermoplastic resin sheet. As a result, the effect of preventing wrinkle skin and wrinkles of the decorative sheet at the time of molding is further ensured, and exudation of additives and low molecular weight components from the thermoplastic resin sheet and thermal discoloration are prevented. Therefore, in the case of a cosmetic material with a mirror surface (smooth) surface, a cosmetic material that does not impair the mirror surface can be obtained , and in the case of a cosmetic material with an uneven pattern surface , the desired uneven pattern is faithfully reproduced. A cosmetic material can be obtained.
[Brief description of the drawings]
1 is a cross-sectional view illustrating a decorative sheet used in the method for producing a thermosetting resin decorative material according to the present invention.
2 is a cross-sectional view schematically showing an example of a thermosetting resin decorative material which is more produced in the present invention.
FIG. 3 is an explanatory view showing a typical method for producing a thermosetting resin decorative material.
Another example of a more manufactured thermosetting resin decorative material to the present invention; FIG is a cross-sectional view schematically showing.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 Decorative sheet 11 Thermoplastic resin sheet 11a Concavity and convexity pattern 12 Fiber sheet 13 Adhesive layer 14 Decoration layer 20 Fiber reinforced thermosetting resin base material 30 Press molding machine 31, 32 type 31a Reverse concavity and convexity 33, 34 Ram 40 SMC

Claims (3)

A decorative sheet in which a fibrous sheet is laminated on one side of a transparent thermoplastic resin sheet having a heat shrinkage rate of 1% or less when heated in a 150 ° C. atmosphere for 30 minutes is prepared. In between, the fiber reinforced thermosetting resin base material and the decorative sheet are placed with the fiber reinforced thermosetting resin base material facing the fiber sheet side of the decorative sheet, and the thermoplastic resin sheet is thermally deformed. by press-forming at a forming temperature set so that the low temperature at least 20 ° higher than the temperature, the thermosetting resin, characterized in Rukoto the decorative sheet is integrally laminated on the surface of the fiber reinforced thermosetting resin base material A method for producing a cosmetic material. The process according to claim 1 thermosetting resin decorative material according to side decorative layer of fibrous sheet of the thermoplastic resin sheet is characterized in that there use a decorative sheet laminated. Process for producing a thermosetting resin decorative material according to claim 1 or claim 2, characterized that you form uneven pattern on the opposite side of the fibrous sheet of the thermoplastic resin sheet by embossing when molding.

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