JP5211478B2 - Decorative sheet for insert molding - Google Patents

Description

  The present invention relates to a decorative sheet, and more specifically, for insert molding that is required to have high design properties such as an interior of a building and an interior of a vehicle and can be suitably used in the field used for insert molding. It relates to a decorative sheet.

  Conventionally, a decorative sheet in which a base sheet, various printed layers, and a surface resin layer are sequentially laminated has been used for decoration of wallpaper, furniture, building materials, etc., and also for interior parts of vehicles. Yes.

  In the field of such decorative sheets, vinyl chloride sheets, vinyl chloride-vinyl acetate copolymer sheets, and the like have been used as base sheets. These sheets have been widely used because they have advantages such as excellent processability, printability, embossability, etc., the hardness can be easily adjusted by the amount of plasticizer added, and they are inexpensive.

  However, when a vinyl chloride sheet or vinyl chloride-vinyl acetate copolymer sheet is used as the base sheet constituting the decorative sheet, there is a risk that harmful gases such as vinyl chloride monomer or chlorine gas may be generated during combustion. At times, there was a problem with concerns about damaging the incinerator used and polluting the environment.

  In order to solve such a problem, at present, the material of the base sheet is made of a non-vinyl chloride material (for example, Patent Documents 1 and 2).

  Patent Document 1 discloses a decorative sheet using a polyolefin-based resin as a base sheet, and Patent Document 2 discloses a decorative sheet using an acrylic resin as a base sheet. .

JP-A-6-16832 Japanese Patent No. 2916130

However, in the decorative sheet disclosed in these patent documents, the performance may not always be sufficient.
For example, currently, when manufacturing various parts for in-house decoration such as automobiles, metallic and wood-tone decorative sheets are often used, and these various parts are preliminarily placed in a mold. Most of these are manufactured by a so-called insert molding method in which the decorative sheet and the parts are integrally formed by injecting a molten resin into a mold and then injecting the resin. When used in such applications, in a decorative sheet using a base sheet as disclosed in the above-mentioned patent document, there arises a problem in adhesion to non-adhering bodies, bending workability, and the like. There were many cases. In the insert molding method, the molten resin at 220 to 240 ° C. is pressed from the base sheet side of the decorative sheet in the mold. At this time, heat from the resin is generated in the decorative sheet. In some cases, the ink in the printed layer flows and the design properties are impaired.

  The present invention has been made in view of such a situation, and no toxic gas such as chlorine gas is generated even during combustion. Therefore, problems such as environmental pollution do not occur, and so-called insert moldability is achieved. The main object is to provide a novel decorative sheet that is excellent and therefore can be suitably used for various interior decorations such as automobiles.

In order to solve the above problems, the present invention is at least a base sheet, a printed layer, and a decorative sheet for insert molding formed by laminating a surface resin layer, wherein the base sheet has a butadiene component ratio. Is a single layer sheet made of ABS resin having a styrene component ratio of 38 to 48% by weight of the whole , and the surface resin layer is made of an acrylic resin having a thickness of 50 to 150 μm. And the said printing layer contains polyester urethane resin as a binder, It is characterized by the above-mentioned.

  Moreover, in said invention, the Vicat softening temperature of the said base material sheet may be 85-100 degreeC, and 1100-2000 Mpa may be sufficient as a curvature elastic modulus.

Moreover, in said invention, the said base material sheet may be ABS resin whose butadiene component ratio is 27 to 30 weight% of the whole.

  According to the invention, at least a base sheet, a printing layer, and a surface resin layer are laminated, and the base sheet has a butadiene component ratio of 10 to 33% by weight of the whole. Therefore, various characteristics of the ABS resin, specifically, rigidity, hardness, workability, impact resistance, bending fatigue, and the like can be imparted to the decorative sheet.

  In addition, according to the above invention, the ABS resin is not simply used, but the proportion of the butadiene component forming the ABS resin is limited to a predetermined value. Here, when a decorative sheet is used in the insert molding method, as described above, the decorative sheet comes into contact with a molten resin at 200 ° C. or higher at the time of insert molding. The moldability can be improved without producing a unique rubber odor derived from the butadiene component contained in the ABS resin as the material sheet. Therefore, it can be suitably used for decorations such as automobile interior panels.

  In addition, since the decorative sheet of the present application limits the thickness of the surface resin layer to 50 to 150 μm, as described above, even when it is in contact with a high-temperature molten resin, the heat from the resin is applied to the decorative sheet. Since it can escape to a metal mold | die without accumulating in an inside, it can prevent that the ink which comprises a printing layer flows with heat, and the designability falls.

  Furthermore, the moldability in insert molding can be further improved by setting the Vicat softening temperature of the base sheet made of the ABS resin to 85 to 100 ° C. and the flexural modulus to 1100 to 2000 MPa.

  In the decorative sheet of the present application, the printed layer can contain at least a thermoplastic resin. As described above, the decorative sheet of the present application can prevent the ink in the printing layer from flowing due to heat, so that a heat-sensitive thermoplastic resin can be used as a binder component and the like. The degree of freedom of selection can be improved. Moreover, by including a thermoplastic resin in the printing layer, the flexibility of the printing layer can be improved, and as a result, the followability of the decorative sheet to the mold during insert molding can be improved. It can be set as a more highly-designed insert molding.

  Hereinafter, the decorative sheet of the present invention will be specifically described with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view for explaining the configuration of the decorative sheet of the present invention.

  As shown in FIG. 1, the decorative sheet 10 of the present invention is configured by laminating a base sheet 11, a printing layer 12, and a surface resin layer 13.

(1) Substrate sheet In the decorative sheet 10 of the present invention, the feature is that the substrate sheet 11 is made of an ABS resin having a butadiene component ratio of 10 to 33% by weight. By using such an ABS resin as a base sheet, it is possible to improve the decorative sheet and various characteristics, particularly insert moldability, and no rubber odor is generated even when used for insert molding. Therefore, it can be suitably used when manufacturing interior parts such as automobiles.

  Here, the ABS resin constituting the base sheet 10 is a copolymer (copolymer) of acrylonitrile, butadiene (Butadiene), and styrene (Styrene).

  In the present invention, the ratio of the butadiene component is limited to the above range. If the butadiene component ratio is less than 10% by weight, the vicat softening temperature of the decorative sheet increases and the flexural modulus increases. When vacuum forming is performed for the purpose, air leakage is worsened, so that a so-called freeze line is likely to appear. Further, when the flexural modulus (rigidity) is high, there is a problem that air is trapped and defective lamination due to talmi tends to occur when dry lamination is performed. On the other hand, if the proportion of the butadiene component exceeds 33% by weight, there is a possibility that a rubber odor may be generated when the decorative sheet is used in the insert molding method, and the linear expansion coefficient increases, and distortion due to shrinkage during molding occurs. There is a possibility that the problem of becoming easy occurs. The proportion of the butadiene component needs to be 10 to 33% by weight, more preferably 24 to 33% by weight, and particularly preferably 27 to 30% by weight based on the whole.

  In the present invention, the butadiene component ratio may be 10 to 33% by weight relative to the whole, and the other component ratios (acrylonitrile and styrene) are not particularly limited, depending on the expected characteristics, It is possible to design appropriately. For example, the acrylonitrile component ratio is preferably 19 to 48% by weight with respect to the whole, while the styrene component ratio is preferably 38 to 48% by weight with respect to the whole. Needless to say, these component ratios need to be set so as to be 100% by weight in total.

  As the base material sheet 11 in the decorative sheet 10 of the present invention, the Vicat softening temperature is preferably 85 to 100 ° C., and the flexural modulus is preferably 1100 to 2000 MPa. By setting the Vicat softening temperature and the flexural modulus to such values, it is possible to improve the properties of the decorative sheet, particularly the insert moldability.

  Here, the Vicat softening temperature means that the medium (heating tub or heating phase) is raised at a constant speed while applying a predetermined load to the test piece placed in the heating tub or heating phase through a needle-like indenter placed vertically. This means the temperature of the medium when the needle-like indenter has penetrated 1 mm into the test piece. In the present invention, it is a value obtained by a measuring method standardized in JIS K 7206.

  If the value of Vicat softening temperature is lower than 85 ° C, so-called crushed skin may occur in the continuous heat resistance test, or heat-resistant creep may decrease. On the other hand, if the value of Vicat softening temperature is higher than 100 ° C, lamination Sometimes air stains occur or foaming occurs during vacuum forming.

  Further, the flexural modulus is a value obtained by a measurement method standardized in ISO 178 in the present invention.

  If the value of the flexural modulus is smaller than 1100 MPa, the rigidity is lowered. On the other hand, if the value of the flexural modulus is greater than 2000 MPa, it may be difficult to remove tarmi during continuous dry lamination. The value of the flexural modulus is preferably in the range of 1100 to 1300 MPa from the viewpoint of rigidity and removal of talmi.

  The thickness of the base sheet 11 in the decorative sheet 10 of the present invention is not particularly limited, and can be appropriately selected depending on the application and the like. For example, it may be about 300 to 700 μm, but about 400 to 600 μm is preferable in consideration of insert moldability.

  In addition, when the entire decorative sheet 10 is thick, not only the cost is increased, but the decorative sheet is pulled by the flow of the molten resin to be injected at the time of insert molding, and wrinkles may occur at both ends. . Accordingly, the overall thickness of the decorative sheet 10 is preferably about 2.5 to 3.0 mm.

(2) Print layer Next, the print layer 12 in the decorative sheet 10 of the present invention will be described.

  The printing layer 12 is a layer formed with ink by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, ink jet printing, and the like. In addition, in the case of a full-surface pattern, it may be formed of a paint by a known coating method such as gravure coating or roll coating.

  The pattern of the printed layer 12 is not particularly limited and can be appropriately selected depending on the application. For example, a wood grain pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, A symbol, a solid surface, etc. can be mentioned. The print layer 12 is also used in combination with a pattern pattern layer that expresses a pattern such as a wood grain pattern and a full surface solid layer. The entire solid layer is usually used as a concealing layer, a colored layer, a colored concealing layer, or the like.

  The printing layer 12 is usually formed on the front side surface of the base sheet 11 as shown in FIG. 1 for printing on the base sheet 1, but is not limited to this mode. It can also be formed on the back surface, both front and back surfaces of the material sheet 11, or on the back side surface, front side surface, front and back both surfaces, etc.

  As the ink or paint used for forming the printing layer 12 constituting the decorative sheet 10 of the present invention, as a binder, a polyester resin, urethane resin, acrylic resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, cellulose resin Alternatively, various types such as chlorinated polyolefin resins such as chlorinated polyethylene and chlorinated polypropylene can be used singly or in combination of two or more, and there is no particular limitation. However, in the present invention, it is preferable to include a thermoplastic resin, and among them, it is preferable to use a polyester / urethane resin. This is because the balance between the thermoplastic behavior of the polyester component and the thermosetting behavior of the urethane component is optimal, and the heat resistance and moldability are also good.

  However, since the chlorinated polyolefin resin becomes a resin containing chlorine, it is preferably not used.

  The colorant used in the ink or paint includes titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone yellow, and Hansa Yellow A. , Quinacridone red, permanent red 4R, organic pigments (including dyes) such as phthalocyanine blue, indanthrene blue RS, aniline black, metal pigments made of metal powder such as aluminum, brass, etc., titanium dioxide coated mica, basic carbonic acid Pearlescent (pearl) pigments, fluorescent pigments and the like made of foil powder such as lead can be used singly or in combination.

  Such a printed layer 12 is one of typical layers formed as a layer for applying a decorative pattern to a decorative sheet. In order to further improve the decorative property of the printed layer 12, a metal thin film layer or the like is used. May be formed. The metal thin film layer can be formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum deposition or sputtering. This metal thin film layer may be provided on the entire surface, or may be provided partially in a pattern.

(3) Surface resin layer Next, the surface resin layer 13 in the decorative sheet 10 of this invention is demonstrated.

  The surface resin layer 13 in the present invention is located on the surface of the decorative sheet 10 and is formed for the purpose of protecting the printing layer 12 and imparting various effects to the decorative sheet 10 depending on the application. Is a layer.

  In the present application, the material or the like is not particularly limited, and various resins can be used. Specifically, for example, resins such as acrylic, polyester, polypropylene, ethylene-vinyl alcohol copolymer, polycarbonate, cellulose triacetate, and the like can be cited. Among them, acrylic is considered in consideration of insert moldability, weather resistance, and surface hardness. It is preferable to use a resin.

  Here, as the acrylic resin, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) propyl acrylate, poly (meth) acrylate butyl, methyl (meth) acrylate / (meth) acrylic Such as butyl acrylate copolymer, (meth) ethyl acrylate / (meth) butyl acrylate copolymer, ethylene / (meth) methyl acrylate copolymer, styrene / (meth) methyl acrylate copolymer, etc. ) An acrylic resin composed of a homopolymer or a copolymer containing an acrylate ester. (However, methyl (meth) acrylate means methyl acrylate or methyl methacrylate, and the following (meth) shall have the same meaning.) In the case of poly (meth) acrylate, the degree of polymerization Is preferably about 900 to 1800, and when the degree of polymerization is larger than this, it is necessary to add a low molecular weight material having an effect of imparting plasticity to lower the heat distortion temperature.

  On the other hand, examples of the polyester resin include polyester resins represented by polyethylene terephthalate, polybutylene terephthalate, ethylene / terephthalate / isophthalate copolymer, and the like. Polyester resins are ester-bonded with aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid as acid components and aliphatic diols such as ethylene glycol, diethylene glycol, butanediol and hexanediol as alcohol components. It is the copolymer obtained by doing.

  In the surface resin layer 13 of the present invention, an ultraviolet absorber and / or a light stabilizer may be added for the purpose of imparting weather resistance (light resistance) to the decorative sheet 10. The addition amount in this case is usually about 0.5 to 10% by weight for both the ultraviolet absorber and the light stabilizer, but it is generally preferable to use the ultraviolet absorber and the light stabilizer in combination. As the ultraviolet absorber, organic substances such as benzotriazole, benzophenone, salicylic acid ester, and triazine, or inorganic substances such as fine particle zinc oxide, cerium oxide, and titanium oxide of 0.2 μm or less can be used. As the stabilizer, a hindered amine radical scavenger such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate or a piperidine radical scavenger can be used.

  Furthermore, powders such as calcium carbonate, barium sulfate, clay, and talc may be added as a filler in addition to the above-described ultraviolet absorber and light stabilizer. The amount added is appropriately determined according to the application. In addition, powders such as aluminum hydroxide and magnesium hydroxide may be added to the colored thermoplastic resin layer as a flame retardant. The addition amount is preferably in the range of 10 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

  The thickness of such a surface resin layer 13 needs to be in the range of 50 to 150 μm. If the thickness is less than 50 μm, it is difficult to exert the effect of the layer. If the thickness is more than 150 μm, the heat from the injection resin is trapped in the decorative sheet in the mold at the time of insert molding, and the ink flow etc. May occur. From the above viewpoint, the thickness of the surface resin layer 13 is preferably 75 to 125 μm.

(4) Other Layers and Various Treatments As described above, the decorative sheet 10 of the present application is composed of at least the base sheet 11, the printing layer 12, and the surface resin layer 13, and constitutes the decorative sheet 10. A layer is not limited to these, According to the use of a decorative sheet, the performance calculated | required, etc., it is also possible to laminate | stack another layer suitably.

  For the purpose of improving the adhesion between the decorative sheet 10 and the adherend, an easy adhesion primer layer (not shown) is placed on the back side of the base sheet 11 (opposite to the surface on which the printing layer is formed). Side).

  As the easy adhesion primer layer, curable resins or thermoplastic resins such as various urethane resins, epoxy resins, thermoplastic polyester resins, and polyamide resins can be used. Among them, two-component curable urethane resins are widely used. It is preferable at the point which can implement | achieve favorable adhesiveness with respect to a to-be-adhered material.

  Further, instead of forming the easy-adhesion primer layer, or in addition to the formation of the easy-adhesion primer layer, an easy-adhesion treatment may be performed on the back surface side of the base sheet 11. Examples of the easy adhesion treatment include corona discharge treatment and ozone treatment.

  Moreover, in the decorative sheet 10 of this invention, you may shape the uneven | corrugated pattern as a decoration process with respect to one part or all part of the various layers which comprise the decorative sheet 10. FIG. By shaping such a concavo-convex pattern, the design of the entire decorative sheet 10 can be further improved.

  This uneven pattern can be shaped by hairline processing, sandblasting, embossing, or the like. For example, embossing is performed by pressing an embossed plate on the surface of a heat-softened resin sheet using a hot press type sheet or a rotary embossing machine. The resin sheet in this case is a surface resin layer or a substrate sheet. Moreover, you may shape the uneven | corrugated pattern simultaneously with film-forming of a base material sheet or a surface resin layer. For example, in a T-die melt extrusion method, an embossing / cooling roller having a concavo-convex pattern on the cooling surface is used as a cooling roller, and the film is formed simultaneously with film formation. Also, the uneven pattern can be shaped by a so-called doubling embossing method in which a base sheet and a surface resin layer are laminated, and at the same time, the surface side of the surface resin layer is shaped by embossing by hot pressure. is there. In addition, as an uneven | corrugated pattern, it is a wood grain board conduit groove | channel, a stone board surface unevenness | corrugation (granite cleaved surface, etc.), cloth surface texture, a satin texture, a grain, a hairline, a ridge line groove, etc. The uneven pattern is usually the front side of the surface resin layer, but may be the back side of the surface resin layer, the front side of the base sheet, or the back side of the base sheet.

  In addition, a colored portion can be formed by filling a colored ink into the concave portion of the concave and convex pattern by a known wiping method (see Japanese Patent Publication No. 58-14312). The same colored ink as that of the printing layer 12 can be used. However, the thing which uses a two-component curable urethane resin as a binder from the point of abrasion resistance is preferable. The wiping method may be any of conventionally used wiping methods such as a doctor blade method and a roll coating method. That is, colored ink is applied to the entire surface of the concavo-convex pattern, and then the ink on the convex portion is scraped off or wiped off with a doctor blade, sponge roll, cloth, etc., so that the colored ink remains in the concave portion.

(5) Adhering body of decorative sheet The adherend (that is, the use of the decorative sheet of the present invention) in which the decorative sheet of the present invention is used is not particularly limited, and can be used for various articles formed by the insert molding method. It is. Resin materials used in the insert molding method include acrylic resins, polyester resins, polystyrene resins, polyolefin resins such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resins, phenol resins, vinyl chloride resins, and cellulose resins. , Rubber materials, resin materials used as three-dimensional shaped articles or sheets, materials combining these two or more materials, for example, wood powder plastic, paper powder plastic, FRP used as plate materials, three-dimensional shaped articles, etc. Examples include composite (element) materials such as (fiber reinforced plastic).

(6) Adhesion (laminate) method to adherend The decorative sheet of the present invention was developed mainly for use in the insert molding method, and therefore the decorative sheet adheres to the adherend. As the (lamination) method, it is preferable to integrally adhere to the surface of the insert molded article at the time of insert molding. Specifically, for example, as described in JP-B-50-19132 and JP-B-43-27488, a decorative sheet is placed between both male and female molds for injection molding, and then a molten resin is molded. For example, an insert molding method in which a decorative sheet is bonded and laminated on the surface of the adherend, which is injected and filled inside, and a molded article, which is a resin molded product, can be used.

Example 1
As a base sheet, an ABS resin having an acrylic component ratio of 28% by weight, a butadiene component ratio of 30% by weight, a styrene component ratio of 42% by weight, and a thickness of 400 μm is prepared. An adhesive mainly composed of polyester / urethane resin was applied to a thickness of 8 μm. On the other hand, a printing layer having a thickness of 5 μm is formed on the back side of an acrylic resin having a thickness of 75 μm as a surface resin layer using a printing ink containing a polyester / urethane resin as a binder component, and then the printing layer is formed. The decorative sheet of Example 1 of the present invention was prepared by laminating the obtained surface protective layer on the adhesive.

Example 2
The above-mentioned examples are all the same except that the composition of the ABS resin as the base sheet is 34% by weight of the acrylic component, 24% by weight of the butadiene component, and 42% by weight of the styrene component. A decorative sheet of Example 2 of the present invention was prepared under the same conditions as in Example 1.

Example 3
All the above examples except that the composition of the ABS resin as the base sheet was 45% by weight of the acrylic component, 15% by weight of the butadiene component, and 40% by weight of the styrene component. A decorative sheet of Example 3 of the present invention was prepared under the same conditions as in Example 1.

Example 4
All the above examples except that the composition of the ABS resin as the base sheet is 42% by weight of the acrylic component, 12% by weight of the butadiene component, and 46% by weight of the styrene component. A decorative sheet of Example 4 of the present invention was prepared under the same conditions as in Example 1.

Example 5
In Example 4, instead of the 75 μm thick acrylic resin used as the surface resin layer, the decorative sheet of Example 5 of the present invention was used in the same manner as in Example 4 except that a 50 μm thick acrylic resin was used. It was created.

Example 6
In Example 1, instead of the acrylic resin having a thickness of 75 μm used as the surface resin layer, a decorative sheet according to Example 6 of the present invention was used in the same manner as in Example 1 except that an acrylic resin having a thickness of 125 μm was used. It was created.

Example 7
All the above examples except that the composition of the ABS resin as the base sheet was 28% by weight of the acrylic component, 27% by weight of the butadiene component, and 45% by weight of the styrene component. A decorative sheet of Example 7 of the present invention was prepared under the same conditions as in 1.

Example 8
All the above examples except that the composition of the ABS resin as the base sheet was 28% by weight of the acrylic component, 33% by weight of the butadiene component, and 39% by weight of the styrene component. A decorative sheet of Example 8 of the present invention was prepared under the same conditions as in No. 1.

Example 9
In Example 7, instead of the 75 μm thick acrylic resin used as the surface resin layer, the decorative sheet of Example 9 of the present invention was used in the same manner as in Example 7 except that a 125 μm thick acrylic resin was used. It was created.

Comparative Example 1
All the above examples except that the composition of the ABS resin as the base sheet is 15% by weight of the acrylic component, 40% by weight of the butadiene component, and 45% by weight of the styrene component. A decorative sheet of Comparative Example 1 was prepared under the same conditions as in Example 1.

Comparative Example 2
All of the above examples except that the composition of the ABS resin as the base sheet is 48% by weight of the acrylic component, 4% by weight of the butadiene component, and 48% by weight of the styrene component. A decorative sheet of Comparative Example 2 was prepared under the same conditions as in 1.

(Comparative test)
1. Flexural Modulus In Examples 1 to 9 and Comparative Examples 1 and 2, the flexural modulus of each ABS resin used as the base sheet was measured using a test method standardized to ISO 178. The results are shown in Table 1 below.

2. Vicat softening temperature In Examples 1 to 9 and Comparative Examples 1 and 2, the Vicat softening temperature was measured using the test method standardized in JIS K 7206 for the ABS resin used as each base sheet. . The results are shown in Table 1 below.

3. Laminate suitability A laminate suitability test was conducted to judge the adhesiveness of each layer constituting the decorative sheets of Examples 1 to 9 and Comparative Examples 1 and 2. This test was evaluated by dry lamination. The dry lamination conditions were a laminating pressure of 4.5 MPa, a tension of 40 kgf, an ABS rush angle of 50 degrees, and an ABS rush temperature of 80 ° C. The results are shown in Table 1 below.

4). Odor In the said Examples 1-9 and Comparative Examples 1-2, in order to judge the rubber odor about the ABS resin used as each base material sheet, the odor test was done. In this test, each ABS resin (30 mm × 10 mm) was placed in a bottle with a height of 100 mm, a diameter of 50 mm, and a mouth diameter of 30 mm, covered, and left at 60 ° C. for 2 hours. I went by sniffing. Open the lid of the bottle, the first person sniffs at a distance of 5 cm from the mouth of the bottle, closes the lid within 5 seconds, heats in the oven for 15 minutes, then the second person sniffs the same, and this is the sixth person Repeat until.
The evaluation was performed in the following 6 stages, and the determination was made based on the average score of 4 persons excluding the upper and lower persons. The results are shown in Table 1 below. In practical use, an evaluation of less than 3 is considered acceptable.
Evaluation 1: Smelly pear Evaluation 2: Feeling smell but not bad smell Evaluation 3: Bad smell Evaluation 4: Very bad smell Evaluation 5: Poisonous smell Evaluation 6: Unbearable smell

5. Insert Moldability Using the decorative sheets of Examples 1 to 9 and Comparative Examples 1 and 2, insert molding was actually performed and comprehensive evaluation was performed. The results are shown in Table 1 below.

6). Surface Hardness About the decorative sheets of Examples 1-9 and Comparative Examples 1-2, the surface hardness was measured using a pencil hardness method specified in JIS. The results are shown in Table 1 below.

* 1 Air stagnation and sagging

  As apparent from Table 1 above, the decorative sheet of the present invention was found to be better in rubber odor, insert moldability and the like than that of the comparative example.

It is a schematic sectional drawing for demonstrating the structure of the decorative sheet of this invention.

Explanation of symbols

10 decorative sheet 11 base sheet 12 printed layer 13 surface resin layer

Claims (3)

At least a decorative sheet for insert molding in which a base sheet, a printing layer, and a surface resin layer are laminated, wherein the base sheet has a butadiene component ratio of 10 to 33% by weight and a styrene component ratio Is a single-layer sheet composed of 38 to 48% by weight of ABS resin, and the surface resin layer is composed of an acrylic resin having a thickness of 50 to 150 μm ,
The printed layer contains a polyester / urethane resin as a binder, and is a decorative sheet for insert molding.   The decorative sheet for insert molding according to claim 1, wherein the base sheet has a Vicat softening temperature of 85 to 100 ° C and a flexural modulus of 1100 to 2000 MPa. The decorative sheet for insert molding according to claim 1 or 2, wherein the base sheet is an ABS resin having a butadiene component ratio of 27 to 30% by weight of the whole.

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