Molded products

Abstract

To provide a molding in which ABS resin or polycarbonate resin is used, and which has excellent chemical resistance, scratch resistance, and water repellency.SOLUTION: There is provided a molding 1 comprising a base material layer 2 and a surface layer 3 laminated on the base material layer 2. The base material layer 2 contains at least one of acrylonitrile-butadiene-styrene resin and polycarbonate resin, and the surface layer 3 contains an alloy resin in which a vinyl chloride resin and a methyl methacrylate resin are blended in a mass ratio of 10:90 to 90:10.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a molded article. [Background technology]

[0002] Generally, acrylonitrile-butadiene-styrene (ABS) resin, polycarbonate resin, etc. are used as molding resins. However, although these general-purpose resins are excellent in terms of moldability and cost, they tend to have low surface hardness and poor scratch resistance. In addition, ABS resins are also poor in chemical resistance.

[0003] Patent Document 1 discloses a molded article having excellent chemical resistance, which is made of a thermoplastic resin composition containing a specific rubber-containing graft copolymer, a vinyl cyanide copolymer, a modified vinyl copolymer, and a polybutylene terephthalate resin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2007-269958 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, the molded article of Patent Document 1 has insufficient surface hardness and poor scratch resistance. Furthermore, in the case of molded articles to be used outdoors in particular, it is also important that the articles have excellent water repellency and are resistant to dirt.

[0006] An object of the present invention is to provide a molded article made of ABS resin or polycarbonate resin, which has excellent chemical resistance, scratch resistance and water repellency. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] A substrate layer and a surface layer laminated on the substrate layer, the base layer contains at least one of an acrylonitrile-butadiene-styrene resin and a polycarbonate resin, The molded article, wherein the surface layer contains an alloy resin in which a vinyl chloride resin and a methyl methacrylate resin are blended in a mass ratio of 10:90 to 90:10. [2] The molded article according to [1], wherein the surface of the surface layer has a pencil hardness of F or more as measured in accordance with JIS K5600-5-4. [3] The molded product according to [1] or [2], wherein the surface layer has a critical strain ε of 0.40% or more as measured in a solvent resistance test using a bending form method. [4] The molded article according to any one of [1] to [3], wherein the surface layer has a water contact angle of 80° or more. Effect of the Invention

[0008] According to the present invention, it is possible to provide a molded article using ABS resin or polycarbonate resin that has excellent chemical resistance, scratch resistance, and water repellency. [Brief description of the drawings]

[0009] [Figure 1] FIG. 2 is a cross-sectional view showing a molded product according to an embodiment of the present invention. [Diagram 2] FIG. 2 is a perspective view showing a test piece used in a solvent resistance test. [Diagram 3] FIG. 1 is a perspective view showing a solvent resistance test. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the molded product of the embodiment will be described with reference to the drawings. Note that the dimensions of the drawings illustrated in the following description are merely examples, and the present invention is not necessarily limited thereto, and can be appropriately modified and implemented within the scope of the present invention.

[0011] 1, the molded article 1 of the embodiment includes a base layer 2 and a surface layer 3 laminated on the base layer 2. That is, the molded article 1 is a laminate including the base layer 2 and the surface layer 3. Although the molded article 1 in this example is in a sheet shape, the shape of the molded article 1 is not limited to a sheet shape. The surface layer 3 may be laminated on only one side of the base layer 2 or on both sides of the base layer 2.

[0012] The base layer 2 is a layer containing at least one of an acrylonitrile-butadiene-styrene (ABS) resin and a polycarbonate (PC) resin. The base layer 2 is preferably a layer containing either an ABS resin or a PC resin. The base layer 2 may contain additives such as a heat stabilizer, a light stabilizer, a lubricant, an ultraviolet absorber, and a filler, as necessary, so long as the effects of the present invention are not impaired.

[0013] The average thickness of the base layer 2 can be appropriately set and can be, for example, 1.0 mm or more and 20 mm or less. The average thickness of the base layer 2 is the average value of thicknesses measured at any five points on the base layer 2.

[0014] The surface layer 3 contains an alloy resin in which a polyvinyl chloride resin (hereinafter referred to as "PVC resin") and a methyl methacrylate resin (hereinafter referred to as "MMA resin") are blended in a mass ratio of 10:90 to 90:10.

[0015] A PVC-based resin is a polymer in which the proportion of repeating units derived from vinyl chloride (hereinafter also referred to as "vinyl chloride units") exceeds 50% by mass relative to the total repeating units. The PVC-based resin may be a homopolymer of vinyl chloride, or a copolymer of vinyl chloride and a vinyl-based monomer copolymerizable with vinyl chloride. When the PVC-based resin is a copolymer, it may be a random copolymer, a block copolymer, or a graft copolymer. The PVC-based resin contained in the alloy resin may be one type, or two or more types.

[0016] The proportion of vinyl chloride units in the PVC resin is preferably 75 mass % or more, more preferably 80 mass % or more, further preferably 85 mass % or more, and particularly preferably 98 mass % or more, based on all repeating units.

[0017] The vinyl monomer copolymerizable with vinyl chloride is not particularly limited, and examples thereof include fatty acid vinyl esters, acrylates, methacrylates, vinyl cyanide, vinyl ethers, α-olefins, unsaturated carboxylic acids or their acid anhydrides, vinylidene chloride, vinyl bromide, various urethanes, and the like.

[0018] Examples of fatty acid vinyl esters include vinyl acetate, vinyl propionate, and vinyl laurate. Examples of acrylates include methyl acrylate, ethyl acrylate, and butyl acrylate. Examples of methacrylates include methyl methacrylate and ethyl methacrylate. Examples of vinyl cyanides include acrylonitrile and methacrylonitrile. Examples of vinyl ethers include vinyl methyl ether, vinyl butyl ether, and vinyl octyl ether. Examples of α-olefins include ethylene, propylene, and butylene. Examples of unsaturated carboxylic acids or their acid anhydrides include acrylic acid, methacrylic acid, and maleic anhydride. The vinyl monomer copolymerizable with vinyl chloride may be used alone or in combination of two or more.

[0019] The average degree of polymerization of the PVC resin is preferably from 400 to 1200, more preferably from 600 to 1000. When the average degree of polymerization of the PVC resin is equal to or higher than the lower limit of the above range, the pencil hardness is improved. When the average degree of polymerization of the PVC resin is equal to or lower than the upper limit of the above range, the molding processability is improved. The average degree of polymerization is measured in accordance with JIS K 6720-2.

[0020] The PVC resin may be either a hard vinyl chloride resin or a soft vinyl chloride resin, but the hard vinyl chloride resin is preferred because it provides a molded product with high surface hardness and excellent scratch resistance.

[0021] The MMA-based resin is a polymer in which the proportion of repeating units derived from methyl methacrylate (MMA) (hereinafter also referred to as "MMA units") is 80% by mass or more relative to the total repeating units. The MMA-based resin may be a homopolymer of MMA, or a copolymer of MMA and a (meth)acrylate other than MMA. Incidentally, (meth)acrylate is a general term for methacrylate and acrylate. When the MMA-based resin is a copolymer, it may be a random copolymer or a block copolymer. The MMA-based resin contained in the alloy resin may be one type or two or more types.

[0022] The proportion of MMA units in the MMA-based resin is preferably 80% by mass or more, more preferably 90% by mass or more, based on all repeating units. When the proportion of MMA units is equal to or more than the lower limit of the above range, moldability is improved.

[0023] Examples of (meth)acrylates other than MMA include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate. The (meth)acrylates other than MMA used in the MMA-based resin may be one type or two or more types.

[0024] The weight average molecular weight of the MMA resin is preferably 10,000 to 600,000, more preferably 20,000 to 400,000. When the weight average molecular weight of the MMA resin is equal to or higher than the lower limit of the above range, the pencil hardness is improved. When the weight average molecular weight of the MMA resin is equal to or lower than the upper limit of the above range, the strength is improved.

[0025] The number average molecular weight of the MMA resin is preferably 5,000 to 300,000, more preferably 10,000 to 200,000. When the number average molecular weight of the MMA resin is equal to or higher than the lower limit of the above range, the pencil hardness is improved. When the number average molecular weight of the MMA resin is equal to or lower than the upper limit of the above range, the strength is improved. The weight average molecular weight and the number average molecular weight are polystyrene-equivalent average molecular weights measured by gel permeation chromatography.

[0026] The melt flow rate (MFR) of the MMA resin is preferably 1.0 g / 10 min or more and 20 g / 10 min or less, more preferably 2.0 g / 10 min or more and 15 g / 10 min or less. When the MFR of the MMA resin is equal to or more than the lower limit of the above range, the processability is good. When the MFR of the MMA resin is equal to or less than the upper limit of the above range, the pencil hardness is improved. The MFR is measured in accordance with JIS K 7210 under conditions of a load of 37.3 N and a temperature of 230°C.

[0027] The mass ratio of the PVC resin to the MMA resin in the alloy resin is 10:90 to 90:10, preferably 30:70 to 70:30, and more preferably 50:50 to 70:30. The higher the ratio of the PVC resin, the higher the solvent resistance. The higher the ratio of the MMA resin, the higher the surface hardness.

[0028] The total proportion of the PVC resin and the MMA resin in the alloy resin is preferably 80 mass % or more, more preferably 85 mass % or more, and even more preferably 90 mass % or more, based on the total mass of the alloy resin. The method for producing the alloy resin is not particularly limited, and any known method can be used.

[0029] Additives such as heat stabilizers, light stabilizers, lubricants, ultraviolet absorbers, and fillers may be added to the alloy resin used for the surface layer 3 as necessary, provided that the effects of the present invention are not impaired. The form of the alloy resin during use is not particularly limited, and may be, for example, in the form of pellets.

[0030] The pencil hardness of the surface of the surface layer 3 is preferably F or more, more preferably H or more. If the pencil hardness is equal to or more than the lower limit, the molded product has excellent scratch resistance. The pencil hardness of the surface of the surface layer 3 can be adjusted by the mass ratio of the PVC resin to the MMA resin in the alloy resin, etc. The pencil hardness is measured in accordance with JIS K5600-5-4.

[0031] The critical strain ε of the surface layer 3 measured in a solvent resistance test by bending form method is preferably 0.40% or more, more preferably 0.60% or more, even more preferably 0.75% or more, and particularly preferably 1.00% or more. When the critical strain ε of the alloy resin is equal to or more than the lower limit, the alloy resin has excellent solvent resistance. The larger the critical strain ε, the better. The critical strain ε of the alloy resin can be adjusted by the mass ratio of the PVC resin and the MMA resin, etc.

[0032] (Solvent resistance test) The critical strain ε of the alloy resin is measured by the following solvent resistance test. As shown in FIG. 2, a rectangular sheet-like test piece 10 having a thickness of 2.0 mm, a width of 30 mm and a length of 125 mm is molded by injection molding using the alloy resin constituting the surface layer 3, and is stored in a desiccator for one day.

[0033] As shown in FIG. 3, jig 100 has the shape of an elliptical cylinder with a major axis 2a of 254 mm and a minor axis 2b of 76.2 mm cut into 1 / 4 by a plane passing through the minor axis and a plane passing through the major axis. It is placed on a horizontal surface with the minor axis (b = 38.1 mm) vertical, the major axis (a = 127 mm) horizontal, and the curved surface 110 facing up. A strip-shaped gauze 20 containing disinfectant ethanol (76.9 to 81.4% by volume at 15 ° C.) is placed in the center of the width direction on the upper surface of the test piece 10 after storage so as to extend in the length direction of the test piece 10, and the gauze 20 on the test piece 10 is covered with a film 30. The first edge 10a in the length direction of the test piece 10 in this state is aligned with the edge 110a on the short axis side of the curved surface 110 of the jig 100, and the test piece 10 is curved so that the lower surface of the test piece 10 is in close contact with the curved surface 110 of the jig 100. In this state, the test piece 10 is left standing for 24 hours under conditions of 23 ° C. and 50% RH. The test piece 10 after standing is removed from the jig 100, and the distance in the length direction between the end closest to the first edge 10a of the crack generated in the test piece 10 and the first edge 10a is defined as d (mm), and the critical strain ε (%) is calculated from the following formula (1). The above measurements are carried out on three molded test pieces, and the average value (%) of the critical strain ε is calculated.

[0034]

number

[0035] In the formula (1), t is the thickness (mm) of the test piece 10.

[0036] The average thickness of the surface layer 3 is preferably 0.2 mm or more and 2.0 mm or less. When the average thickness of the surface layer 3 is equal to or more than the lower limit of the above range, the molded article 1 has excellent scratch resistance even if the base layer 2 is easily scratched. When the average thickness of the surface layer 3 is equal to or less than the upper limit of the above range, the moldability is excellent. The average thickness of the surface layer 3 is an average value of thicknesses measured at any five points on the surface layer 3.

[0037] The water contact angle of the surface of the surface layer 3 is preferably 80° or more, more preferably 85° or more, even more preferably 90° or more, particularly preferably 93° or more, and most preferably 95° or more. If the water contact angle of the surface of the surface layer 3 is equal to or more than the lower limit, the water repellency is excellent and the molded article 1 is less likely to become dirty. The upper limit of the water contact angle of the surface of the surface layer 3 is not particularly limited, but the substantial upper limit is about 120°.

[0038] The water contact angle on the surface of the surface layer 3 is a value measured by the following method. Approximately 10 μL of pure water is dropped onto any five points on the surface of the surface layer 3, and the contact angle one second after dropping (static contact angle) is measured according to the θ / 2 method (θ / 2=arctan(h / r), θ: contact angle, r: droplet radius, h: droplet height), and the average of these values ​​is defined as the water contact angle. The atmosphere during the contact angle measurement is a temperature of 23°C±5°C and a relative humidity of 40 to 65%. The object to be measured is left in the atmosphere for 10 minutes or more before dropping pure water and measuring.

[0039] For example, in the case of a sheet, the average thickness of the molded article 1 can be set to 1.0 mm or more and 20 mm. The average thickness of the molded article 1 is the average value of thicknesses measured at any five points on the surface layer 3.

[0040] The method for producing the molded product of the present invention is not particularly limited. For example, a method of forming a surface layer by injection molding, and then molding a base layer by injection molding with the surface layer inserted therein, a method of forming a two-layer structure by extruding the base layer and the surface layer using a main extruder and a sub-extruder, respectively, etc. can be mentioned. In addition, in the case of a sheet-shaped molded product, it can also be molded into a desired shape by compressed air molding.

[0041] As described above, the molded article of the present invention has a surface layer containing an alloy resin in which a PVC resin and an MMA resin are blended at a specific mass ratio on a substrate layer containing an ABS resin or a PC resin, and thus has excellent solvent resistance, scratch resistance, and water repellency. The uses of the molded article of the present invention are not particularly limited, and examples thereof include vehicles, building materials, and home appliances.

[0042] The technical scope of the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention. For example, the molded article of the present invention may have another layer between the substrate layer and the surface layer. EXAMPLES

[0043] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following description.

[0044] [Pencil hardness] The pencil hardness was measured in accordance with JIS K5600-5-4.

[0045] [Solvent resistance test] Using the alloy resin forming the surface layer of each example, a rectangular sheet-like test piece 10 having a thickness of 2.0 mm, a width of 30 mm, and a length of 125 mm was molded by injection molding, as shown in Figure 2, and stored in a desiccator for one day. As shown in FIG. 3, a jig 100 having a shape of an elliptical cylinder with a major axis 2a of 254 mm and a minor axis 2b of 76.2 mm cut into 1 / 4 by a plane passing through the minor axis and a plane passing through the major axis was placed on a horizontal surface with the minor axis (b = 38.1 mm) in the vertical direction, the major axis (a = 127 mm) in the horizontal direction, and the curved surface 110 facing up. A strip-shaped gauze 20 containing disinfectant ethanol (76.9 to 81.4% by volume at 15°C) was placed in the center of the width direction on the upper surface of the test piece 10 after storage so as to extend in the length direction of the test piece 10. The gauze 20 on the test piece 10 was covered with Saran Wrap (registered trademark) which is a film 30. The first edge 10a in the length direction of the test piece 10 in this state was aligned with the edge 110a on the short axis side of the curved surface 110 of the jig 100, and the test piece 10 was curved so that the lower surface of the test piece 10 was in close contact with the curved surface 110 of the jig 100, and the test piece 10 was left standing for 24 hours under conditions of 23°C and 50% RH. The test piece 10 after standing was removed from the jig 100, and the distance in the length direction between the end of the crack generated in the test piece 10 closest to the first edge 10a and the first edge 10a was defined as d (mm), and the critical strain ε (%) was calculated from the above formula (1). The above measurements were carried out on three molded test pieces, and the average value (%) of the critical strain ε was calculated. In addition, when the crack generation distance d at a thickness of 2.0 mm is 105 mm or more, the critical strain ε is set to "1.00 (%) or more."

[0046] [Water contact angle] The molded article of each example was left for 10 minutes or more in an atmosphere of 23°C ± 5°C temperature and 40 to 65% relative humidity. Next, about 10 μL of pure water was dropped on the surface of the surface layer side of the molded article in the above atmosphere, and the contact angle (static contact angle) 1 second after the drop was measured according to the θ / 2 method (θ / 2 = arctan (h / r), θ: contact angle, r: droplet radius, h: droplet height). The water contact angle was measured at any five points on the surface of the surface layer side of the molded article, and the average value was taken as the water contact angle of the surface of the surface layer. A contact angle meter "LSE-A100" manufactured by NIC was used to measure the contact angle.

[0047] [Example 1] As the molding material for the surface layer, 90 parts by mass of PVC resin (ratio of vinyl chloride units: 87% by mass, average polymerization degree: 700) and 10 parts by mass of MMA resin (trade name "Acrypet VH-001", manufactured by Mitsubishi Chemical Corporation, ratio of MMA units: 90% by mass, weight average molecular weight: 90,000, number average molecular weight: 50,000, MFR: 2.0 g / 10 min) were used, and a sheet-like surface layer having a thickness of 1.0 mm, a width of 30 mm, and a length of 125 mm was produced by injection molding. Next, as the molding material for the base layer, PC resin (trade name "SD Polyca 301-10", manufactured by Sumika Styron Polycarbonate Co., Ltd.) was used, and a sheet-like molded product having a thickness of 2.0 mm, a width of 30 mm, and a length of 125 mm was produced by injection molding in which the surface layer was inserted into an injection molding die. It should be noted that Example 1 is a reference example.

[0048] [Example 2] A molded product was produced in the same manner as in Example 1, except that the mass ratio of the PVC-based resin and the MMA-based resin in the alloy resin forming the surface layer was changed to 70:30, the thickness of the surface layer was changed to 0.5 mm, and the molding material of the base layer was changed to ABS resin (product name "Techno ABS 130", manufactured by Techno Polymer Co., Ltd.).

[0049] [Example 3] A molded article was produced in the same manner as in Example 1, except that the mass ratio of the PVC-based resin and the MMA-based resin in the alloy resin forming the surface layer was changed to 50:50.

[0050] [Example 4] A molded article was produced in the same manner as in Example 1, except that the mass ratio of the PVC resin and the MMA resin in the alloy resin forming the surface layer was changed to 50:50 and the thickness of the surface layer was changed to 0.5 mm.

[0051] [Example 5] A molded article was produced in the same manner as in Example 2, except that the mass ratio of the PVC-based resin and the MMA-based resin in the alloy resin forming the surface layer was changed to 30:70. It should be noted that Example 5 is a reference example.

[0052] [Example 6] A molded article was produced in the same manner as in Example 2, except that the mass ratio of the PVC-based resin and the MMA-based resin in the alloy resin forming the surface layer was changed to 10:90. It should be noted that Example 6 is a reference example.

[0053] [Comparative Example 1] A molded article was produced in the same manner as in Example 2, except that the mass ratio of the PVC-based resin and the MMA-based resin in the molding material for the surface layer was changed to 100:0.

[0054] [Comparative Example 2] A molded article was produced in the same manner as in Example 2, except that the mass ratio of the PVC-based resin and the MMA-based resin in the molding material for the surface layer was changed to 0:100.

[0055] [Comparative Example 3] A sheet-like molded product having a thickness of 2.0 mm was produced in the same manner as in Example 1, except that no surface layer was formed on the base layer.

[0056] [Comparative Example 4] A sheet-like molded product having a thickness of 2.0 mm was produced in the same manner as in Example 2, except that no surface layer was formed on the base layer.

[0057] The results for each example are shown in Table 1.

[0058] [Table 1]

[0059] As shown in Table 1, in Examples 1 to 6 in which a surface layer containing an alloy resin in which PVC-based resin and MMA-based resin were blended in a specific ratio was formed on a base layer containing ABS resin or PC resin, the surface of the surface layer had high pencil hardness, excellent scratch resistance, excellent solvent resistance, and a high water contact angle, resulting in excellent water repellency. On the other hand, in Comparative Example 1, in which the surface layer was formed only with a PVC-based resin, the pencil hardness of the surface of the surface layer was low and the scratch resistance was poor. In Comparative Example 2, in which the surface layer was formed only with an MMA-based resin, the solvent resistance of the surface layer was poor. In Comparative Example 3, in which no surface layer was formed on the base layer containing a PC resin, the pencil hardness of the surface was low and the scratch resistance was poor, and the water contact angle was small and the water repellency was also poor. In Comparative Example 4, in which no surface layer was formed on the base layer containing an ABS resin, the pencil hardness of the surface was low and the scratch resistance was poor, the solvent resistance was poor, and the water contact angle was small and the water repellency was also poor. [Explanation of symbols]

[0060] 1...molded article, 2...base material layer, 3...surface layer, 10...test piece, 20...gauze, 30...film , 100...jig, 110...curved surface.

Claims

1. A substrate layer and a surface layer laminated on the substrate layer, the base layer contains at least one of an acrylonitrile-butadiene-styrene resin and a polycarbonate resin, the surface layer contains an alloy resin in which a vinyl chloride resin and a methyl methacrylate resin are blended in a mass ratio of 50:50 to 70:30; The weight average molecular weight of the methyl methacrylate-based resin is 10,000 or more and 600,000 or less, The average thickness of the surface layer is 0.2 mm or more and 2.0 mm or less, A molded article in which the water contact angle of the surface of the surface layer is 93° or more (excluding those in which 5 to 45 parts by weight of an inorganic filler is blended with 100 parts by weight of a base resin consisting of 50 to 90% by weight of vinyl chloride resin and 5 to 50% by weight of acrylic resin).

2. The molded article according to claim 1, wherein the surface of the surface layer has a pencil hardness of F or more as measured in accordance with JIS K5600-5-4.

3. The molded product according to claim 1 or 2, wherein the surface layer has a critical strain ε of 0.40% or more as measured in a solvent resistance test by a bending form method.

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