WO2021241732A1 - Alloy resin and shaped article - Google Patents

Abstract

An alloy resin usable for forming a surface layer of a shaped article comprising a base layer and the surface layer, the alloy resin comprising the vinyl-chloride-based resin and the methyl-methacrylate-based resin in a mass ratio of 20:80 to 90:10. When the ratio (W) of the mass of the methyl-methacrylate-based resin to the total mass of the vinyl-chloride-based resin and the methyl-methacrylate-based resin is plotted as the abscissa and the melt flow rate (R) of the alloy resin, measured in accordance with JIS K 7210-1, is plotted as the ordinate to obtain a graph, then the plots lie in a range sandwiched between a line represented by R=6.25-4.7×W and a line represented by R=4.50-4.7×W.

Description

Alloy resin and molded products

The present invention relates to alloy resins and molded articles.
This application claims priority based on Japanese Patent Application No. 2020-094194 filed in Japan on May 29, 2020, the contents of which are incorporated herein by reference.

Generally, polypropylene, acrylonitrile-butadiene-styrene (ABS) resin, or the like is used as the molding resin. These general-purpose resins are excellent in moldability and cost, but tend to have low surface hardness and inferior scratch resistance. Acrylic resin and rigid vinyl chloride resin are known as resins having excellent scratch resistance. Rigid vinyl chloride resins are generally excellent in flame retardancy and solvent resistance, and are therefore widely used in pipes, general building materials, and the like.

It is also known to add an acrylic resin as an alloy to a vinyl chloride resin for the purpose of improving the heat resistance of the rigid vinyl chloride resin (for example, Patent Document 1). Further, as a molded product having designability, impact strength, weather resistance, and solvent resistance, a laminate in which a transparent resin layer (surface layer) using an acrylic resin is provided on a base material layer is disclosed (patented). Document 2).

Japanese Unexamined Patent Publication No. 61-014246 Japanese Unexamined Patent Publication No. 2007-313902

However, it is difficult to achieve both transparency and impact resistance with an alloy resin of a vinyl chloride resin and an acrylic resin as in Patent Document 1. Further, in the laminated body of Patent Document 2, since the surface hardness is lowered, it is difficult to achieve both scratch resistance and impact resistance at the same time.

An object of the present invention is to provide a molded product having solvent resistance, scratch resistance, impact resistance, and transparency, and an alloy resin used for the molded product.

The present invention has the following aspects.
[1] An alloy resin in which a vinyl chloride resin and a methyl methacrylate resin are blended, wherein the mass ratio of the vinyl chloride resin to the methyl methacrylate resin is 20:80 to 90:10, and the mass ratio is 20:80 to 90:10. The ratio (W) of the mass of the methyl methacrylate-based resin to the total mass of the vinyl chloride-based resin and the methyl methacrylate-based resin and the melt flow rate (R) of the alloy resin measured according to JIS K 7210-1 are calculated. , When the ratio (W) is plotted on the horizontal axis and the melt flow rate (R) is plotted on the vertical axis, the plots are represented by the straight line represented by the following formula (1) and the following formula (2). Alloy resin in the area sandwiched by straight lines.
R = 6.25-4.7 × W ・ ・ ・ (1)
R = 4.50-4.7 × W ・ ・ ・ (2)
[2] The alloy resin according to [1], wherein the pencil hardness measured according to JIS K5600-5-4 is F or more.
[3] The alloy resin according to [1] or [2], wherein the critical strain ε measured in the solvent resistance test by the bending foam method is 0.45% or more.
[4] The alloy resin according to any one of [1] to [3], wherein the Charpy impact strength measured according to JIS K7111-1 is 5.0 kJ / m ^{2 or more.}
[5] The base material comprises a base material layer and a surface layer laminated on the base material layer, and the surface layer contains the alloy resin according to any one of [1] to [4]. The layer contains a transparent resin and an impact resistance improving agent, and the content of the impact resistance improving agent in the base material layer is 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the transparent resin. Is a molded product.

According to the present invention, it is possible to provide a molded product having solvent resistance, scratch resistance, impact resistance, and transparency, and an alloy resin used for the molded product.

It is sectional drawing which showed the molded article of an Example. It is a perspective view which showed the test piece used for the solvent resistance test. It is a perspective view which showed the state of the solvent resistance test. It is a figure which plotted the melt flow rate (R) measured for each ratio (W) in Experimental Example 1 on the graph with the ratio (W) as the horizontal axis, and the melt flow rate (R) as the vertical axis.

Hereinafter, the molded product of the embodiment will be described with reference to the drawings. It should be noted that the dimensions and the like of the figures exemplified in the following description are examples, and the present invention is not necessarily limited to them, and the present invention can be appropriately modified without changing the gist thereof. ..

[Molding]
As shown in FIG. 1, the molded product 1 of the embodiment includes a base material layer 2 and a surface layer 3 laminated on the base material layer 2. That is, the molded product 1 is a laminated body including the base material layer 2 and the surface layer 3. The surface layer 3 contains an alloy resin.

(Alloy resin)
The alloy resin is a mixture of a vinyl chloride resin (hereinafter referred to as "PVC resin") and a methyl methacrylate resin (hereinafter referred to as "MMA resin") in a mass ratio of 20:80 to 90:10. Has been done. Further, the ratio (W) of the mass of the MMA-based resin to the total mass of the PVC-based resin and the MMA-based resin and the melt flow rate (R) of the alloy resin measured according to JIS K 7210-1 are the ratio (W). Is plotted on the horizontal axis and the melt flow rate (R) is plotted on the vertical axis. At this time, the plot of the melt flow rate (R) with respect to the ratio (W) is represented by a straight line represented by the following formula (1) (hereinafter, also referred to as “straight line (1)”) and the following formula (2). It is in a region (hereinafter, also referred to as “region A”) sandwiched between straight lines (hereinafter, also referred to as “straight line (2)”). However, the ratio (W) is a value obtained by dividing the mass of the MMA-based resin by the total mass of the PVC-based resin and the MMA-based resin, and satisfies 0.2 ≦ ratio (W) ≦ 0.8.
R = 6.25-4.7 × W ・ ・ ・ (1)
R = 4.50-4.7 × W ・ ・ ・ (2)

Hereinafter, the melt flow rate is also referred to as “MFR”.
The MFR (R) of the alloy resin is preferably 1.0 g / 10 minutes or more and 5.8 g / 10 minutes or less, and more preferably 1.5 g / 10 minutes or more and 5.5 g / 10 minutes or less. When the MFR (R) of the alloy resin is at least the lower limit of the above range, the workability is good. When the MFR (R) of the alloy resin is not more than the upper limit of the above range, the pencil hardness is improved. The MFR (R) is measured in accordance with JIS K 7210 under the conditions of a load of 10 kg (98N) and a temperature of 200 ° C.

The PVC resin is a polymer in which the ratio of repeating units derived from vinyl chloride (hereinafter, also referred to as "vinyl chloride unit") exceeds 50% by mass with respect to all repeating units. The PVC-based resin may be a homopolymer of vinyl chloride, or may be 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 kind or two or more kinds.

The ratio of the vinyl chloride unit in the PVC resin is preferably 75% by mass or more, more preferably 80% by mass or more, further preferably 85% by mass or more, and particularly preferably 98% by mass or more with respect to all the repeating units.

The vinyl-based monomer copolymerizable with vinyl chloride is not particularly limited, and for example, fatty acid vinyl ester, acrylate, methacrylate, vinyl cyanide, vinyl ether, α-olefin, unsaturated carboxylic acid or its acid anhydride, Examples thereof include vinylidene chloride, vinyl bromide, and various types of urethane.

Examples of the fatty acid vinyl ester include vinyl acetate, vinyl propionate, vinyl laurate and the like. Examples of the acrylate include methyl acrylate, ethyl acrylate, butyl acrylate and the like. Examples of the methacrylate include methyl methacrylate and ethyl methacrylate. Examples of vinyl cyanide include acrylonitrile and methacrylonitrile. Examples of the vinyl ether include vinyl methyl ether, vinyl butyl ether, vinyl octyl ether and the like. Examples of the α-olefin include ethylene, propylene and butylene. Examples of unsaturated carboxylic acids or acid anhydrides thereof include acrylic acid, methacrylic acid, maleic anhydride and the like.
As the vinyl-based monomer copolymerizable with vinyl chloride, one type may be used alone, or two or more types may be used in combination.

The average degree of polymerization of the PVC resin is preferably 400 or more and 1200 or less, and more preferably 600 or more and 1000 or less. When the average degree of polymerization of the PVC resin is at least the lower limit of the above range, the pencil hardness is improved. When the average degree of polymerization of the PVC resin is not more than the upper limit of the above range, the molding processability is improved.
The average degree of polymerization is measured according to JIS K 6720-2.

The PVC-based resin may be a hard vinyl chloride resin or a soft vinyl chloride resin, but the hard vinyl chloride-based resin is preferable because the surface hardness of the molded product is high and the scratch resistance is excellent. ..

The MMA-based resin is a polymer in which the ratio of repeating units (hereinafter, also referred to as “MMA units”) derived from methyl methacrylate (MMA) is 80% by mass or more with respect to all repeating units. The MMA-based resin may be a homopolymer of MMA, or may be a copolymer of MMA and a (meth) acrylate other than MMA. In addition, (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 kind or two or more kinds.

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

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) acrylate other than MMA used for the MMA-based resin may be one kind or two or more kinds.

The weight average molecular weight of the MMA resin is preferably 10,000 or more and 600,000 or less, and more preferably 20,000 or more and 400,000 or less. When the weight average molecular weight of the MMA resin is at least the lower limit of the above range, the pencil hardness is improved. When the weight average molecular weight of the MMA resin is not more than the upper limit of the above range, the strength is improved.

The number average molecular weight of the MMA resin is preferably 5,000 or more and 300,000 or less, and more preferably 10,000 or more and 200,000 or less. When the number average molecular weight of the MMA resin is at least the lower limit of the above range, the pencil hardness is improved. When the number average molecular weight of the MMA resin is not more 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 using gel permeation chromatography.

The MFR of the MMA resin is preferably 1.0 g / 10 minutes or more and 20 g / 10 minutes or less, and more preferably 2.0 g / 10 minutes or more and 15 g / 10 minutes or less. When the MFR of the MMA-based resin is at least the lower limit of the above range, the workability is good. When the MFR of the MMA resin is not more than the upper limit of the above range, the pencil hardness is improved. The MFR of the MMA resin is measured under the conditions of a load of 37.3 N and a temperature of 230 ° C. in accordance with JIS K7210.

The mass ratio of the PVC resin and the MMA resin in the alloy resin is 20:80 to 90:10, preferably 30:70 to 70:30, and even more preferably 50:50 to 70:30. The higher the proportion of the PVC resin, the better the solvent resistance and impact resistance. The higher the proportion of MMA-based resin, the higher the surface hardness.

The total ratio of the PVC-based resin and the MMA-based resin in the alloy resin is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, based on the total mass of the alloy resin.
The method for producing the alloy resin is not particularly limited, and a known method can be adopted.

To the alloy resin used for the surface layer 3, additives such as a heat stabilizer, a light stabilizer, a lubricant, an ultraviolet absorber, and a filler may be added as needed, as long as the effects of the present invention are not impaired. can.
The form of the alloy resin at the time of use is not particularly limited, and for example, pellets can be exemplified.

The pencil hardness of the alloy resin and the pencil hardness of the surface of the surface layer 3 are preferably F or higher, more preferably H or higher. When the pencil hardness of the alloy resin is at least the above lower limit value, the pencil hardness of the surface of the surface layer 3 is improved, and the scratch resistance of the molded product is excellent. The pencil hardness of the surface of the alloy resin and the surface layer 3 can be adjusted by the mass ratio of the PVC resin and the MMA resin in the alloy resin and the like.
The pencil hardness is measured according to JIS K5600-5-4.

The critical strain ε measured by the solvent resistance test of the alloy resin constituting the surface layer 3 by the bending foam method is preferably 0.45% or more, more preferably 0.70% or more, and further preferably 1.0% or more. preferable. When the critical strain ε of the alloy resin is at least the above lower limit value, the solvent resistance is excellent. 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.

(Solvent resistance test)
The critical strain ε of the alloy resin is measured by the solvent resistance test shown below.
As shown in FIG. 2, a rectangular plate-shaped test piece 10 having a thickness of 1.5 mm, a width of 30 mm, and a length of 125 mm is molded by an injection molding method using an alloy resin constituting the surface layer 3, and is formed in a desiccator. Store for 1 day.

As shown in FIG. 3, an elliptical column having a major axis 2a of 254 mm and a minor axis 2b of 76.2 mm is cut into quarters on a surface passing through the minor axis and a surface passing through the major axis. It is installed on a horizontal plane so that the shaft (b = 38.1 mm) is in the vertical direction, the long axis (a = 127 mm) is in the horizontal direction, and the curved surface 110 is on the top.
A band-shaped gauze 20 containing disinfectant ethanol (76.9 to 81.4% by volume at 15 ° C.) extends in the length direction of the test piece 10 at the center of the upper surface of the test piece 10 after storage in the width direction. The gauze 20 on the test piece 10 is covered with the film 30. The first edge 10a of the test piece 10 in this state in the length direction is aligned with the edge 110a on the short axis side of the curved surface 110 of the jig 100, and the lower surface of the test piece 10 is in close contact with the curved surface 110 of the jig 100. With the test piece 10 curved as described above, the test piece 10 is allowed to stand for 24 hours under the 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 of the crack generated in the test piece 10 on the side closest to the first edge 10a and the first edge 10a is d (mm). ), And the critical strain ε (%) is calculated from the following equation (3). The above measurement is performed on three molded test pieces, and the average value (%) of the critical strain ε is obtained.

However, in the formula (3), t is the thickness (mm) of the test piece 10.

Charpy impact strength of the alloy resin is preferably 5.0 kJ / ^{m 2} or more, more preferably 8.0kJ / ^{m 2} or more, 15 kJ / ^{m 2} or more is more preferable. When the Charpy impact strength of the alloy resin is at least the lower limit of the above range, the impact resistance of the molded product is improved, and it becomes easy to prevent the molded product from being damaged during use. ^{The Charpy impact strength of the alloy resin is preferably 25 kJ / m 2} or less in terms of excellent durability, thin wall thickness, and excellent weight reduction.
The Charpy impact strength of the alloy resin is measured according to JIS K 711-1.

The tensile strength of the alloy resin is preferably 60 MPa or more and 90 MPa or less, and more preferably 62 MPa or more and 80 MPa or less. When the tensile strength of the alloy resin is at least the lower limit of the above range, the pencil hardness of the molded product is improved. When the tensile strength of the alloy resin is not more than the upper limit of the above range, the workability of the molded product is good. The tensile strength of the alloy resin can be adjusted by injection molding processing conditions and the like.
The tensile strength of the alloy resin is measured according to JIS K7127.

The base material layer 2 contains a transparent resin and an impact resistance improving agent. However, in the present invention, "transparent" means that the haze is 20% or less.

Examples of the transparent resin include PVC-based resin, polystyrene-based resin (hereinafter referred to as "PS-based resin"), MMA-based resin (polymethylmethacrylate, etc.) and the like. Among them, PVC-based resins are preferable because they have good adhesion to the surface layer 3, and when the processing temperature at the time of molding is close between the surface layer 3 and the base layer 2, the moldability becomes easy and the multi-layering is easy. The based resin is more preferable. The transparent resin contained in the base material layer 2 may be one kind or two or more kinds.

As the PVC-based resin and MMA-based resin that can be used as the transparent resin of the base material layer 2, for example, the same PVC-based resin and MMA-based resin exemplified in the description of the surface layer 3 can be exemplified, and the preferred embodiments are also the same. ..

The PS-based resin is a polymer in which the ratio of repeating units derived from styrene (hereinafter, also referred to as "styrene unit") is more than 70% by mass with respect to all repeating units. The PS-based resin may be a homopolymer of styrene, or may be a copolymer of styrene and a vinyl-based monomer copolymerizable with styrene. When the PS-based resin is a copolymer, it may be a random copolymer, a block copolymer, or a graft copolymer.

The ratio of the styrene unit in the PS-based resin is preferably 77% by mass or more, more preferably 82% by mass or more, further preferably 87% by mass or more, and particularly preferably 90% by mass or more, based on all the repeating units.
The vinyl-based monomer copolymerizable with styrene is not particularly limited, and examples thereof include the same vinyl-based monomers copolymerizable with vinyl chloride exemplified in the PVC-based resin.

The impact resistance improving agent is preferably a rubber-containing polymer obtained by polymerizing a vinyl-based monomer in the presence of rubber from the viewpoint of excellent impact resistance and flexural modulus of the molded product.

The rubber is not particularly limited, and is, for example, a silicone rubber made from organosiloxane or the like, an acrylic rubber made from an alkyl acrylate or an alkyl methacrylate as a raw material, a conjugated diene rubber made from butadiene or isoprene as a raw material, and a composite rubber thereof. And so on. These rubbers may be used alone or in combination of two or more. Among these rubbers, acrylic rubber and silicone rubber are preferable from the viewpoint of excellent heat resistance of the molded product, and silicone rubber is more preferable to be contained from the viewpoint of excellent impact resistance of the molded product at low temperature. Composite rubber is more preferred.

Examples of the vinyl-based monomer used in the rubber-containing polymer include aromatic vinyl compounds (styrene, α-methylstyrene, etc.), acrylates (methyl acrylate, ethyl acrylate, etc.), methacrylates (methyl methacrylate, ethyl methacrylate, etc.), and the like. Examples thereof include vinyl cyanide compounds (acrylonitrile, etc.). These vinyl-based monomers may be used alone or in combination of two or more. As the vinyl-based monomer used in the rubber-containing polymer, it is preferable to use styrene and methylmethacrylate as main components, and it is more preferable to use methylmethacrylate as the main component, because the impact resistance improving agent is easy to handle. preferable. However, "mainly composed of a specific vinyl-based monomer" means that the ratio of the mass of the specific vinyl-based monomer unit to the total mass of the vinyl-based monomer unit is 50% by mass or more. means.

As the impact resistance improving agent, a commercially available product may be used. Specifically, as commercially available products of the silicone-acrylic composite rubber-based impact resistance improving agent, for example, S-2001, S-2006, S-2030, S-2100, SRK200A, SX-006, SX-005 and the like. Metabren (trade name, manufactured by Mitsubishi Chemical Corporation) S type and the like. Examples of commercially available acrylic rubber-based impact resistance improving agents include Metabrene (trade name, manufactured by Mitsubishi Chemical Corporation) W type such as W-450A, W-300A, and W-600A. Examples of commercially available butadiene rubber-based impact resistance improving agents include Metabrene (trade name, manufactured by Mitsubishi Chemical Corporation) C type such as C-223A, C-215A, C-201A, and C-140A. ..
The impact resistance improving agent contained in the base material layer 2 may be one kind or two or more kinds.

The content of the impact resistance improving agent in the base material layer 2 is 3 parts by mass or more and 20 parts by mass or less, and 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the transparent resin in the base material layer 2. Is preferable. When the content of the impact resistance improving agent is within the above range, the impact resistance and flexural modulus of the molded product are excellent. When the content of the impact resistance improving agent is at least the lower limit of the above range, the impact resistance of the molded product is improved and damage during use can be prevented. When the content of the impact resistance improving agent is not more than the upper limit of the above range, the pencil hardness of the surface is improved, the appearance is excellent, and the molded product is durable.

Charpy impact strength of the molded article 1 is preferably 5.0 kJ / ^{m 2} or more, more preferably 8.0kJ / ^{m 2} or more, 15 kJ / ^{m 2} or more is more preferable. When the Charpy impact strength is not less than the lower limit of the above range, it becomes easy to prevent damage during use when handling the molded product. ^{The Charpy impact strength is preferably 25 kJ / m 2} or less in terms of excellent durability, thin wall thickness, and excellent weight reduction.
The Charpy impact strength is measured according to JIS K 711-1.

The transparency of the molded product 1 can be determined by measuring the haze. The haze of the molded product is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less. If the haze is equal to or less than the upper limit, the transparency is excellent.
The haze is measured according to JIS K7361.

The average thickness of the molded product 1 is preferably 3.0 mm or more and 6.0 mm or less. The average thickness of the base material layer 2 is preferably 2.0 mm or more and 4.5 mm. The average thickness of the surface layer 3 is preferably 1.0 mm or more and 1.5 mm or less.

The method for producing the molded product of the present invention is not particularly limited. For example, a method in which a surface layer is formed by injection molding and a base material layer is formed by injection molding in which the surface layer is inserted, while extruding the base material layer and the surface layer using a main extruder and a sub-extruder, respectively. Examples include a method of forming two layers.

As described above, in the molded product of the present invention, the PVC-based resin and the MMA-based resin are blended in a specific mass ratio on the base material layer in which the impact resistance improving agent is blended in the transparent resin in a specific ratio. A surface layer containing the obtained alloy resin is laminated. The molded product of the present invention has solvent resistance, scratch resistance, impact resistance, and transparency by laminating such a base material layer and a surface layer.
The use of the molded product of the present invention is not particularly limited, and examples thereof include vehicles, building materials, and home appliances.

The technical scope of the present invention is not limited to the above-described embodiment, and various changes can be made without departing from the spirit of the present invention.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following description.

[Pencil hardness]
The pencil hardness of the surface of the surface layer was measured according to JIS K5600-5-4.

[Solvent resistance test]
In each example, as shown in FIG. 2, a rectangular plate-shaped test piece 10 having a thickness of 1.5 mm, a width of 30 mm, and a length of 125 mm is molded by an injection molding method using an alloy resin forming a surface layer. , Stored in a desiccator for one day.
As shown in FIG. 3, an elliptical column having a major axis 2a of 254 mm and a minor axis 2b of 76.2 mm is cut into quarters on a surface passing through the minor axis and a surface passing through the major axis. It was installed on a horizontal plane so that the shaft (b = 38.1 mm) was in the vertical direction, the long axis (a = 127 mm) was in the horizontal direction, and the curved surface 110 was on the top.
A band-shaped gauze 20 containing disinfectant ethanol (76.9 to 81.4% by volume at 15 ° C.) extends in the length direction of the test piece 10 at the center of the upper surface of the test piece 10 after storage in the width direction. I installed it like this. The gauze 20 on the test piece 10 was covered with Saran Wrap®, which is a film 30. The first edge 10a of the test piece 10 in this state in the length direction is aligned with the edge 110a on the short axis side of the curved surface 110 of the jig 100, and the lower surface of the test piece 10 is in close contact with the curved surface 110 of the jig 100. The test piece 10 was allowed to stand for 24 hours under the conditions of 23 ° C. and 50% RH in a curved state. The test piece 10 after standing is removed from the jig 100, and the distance in the length direction between the end of the crack generated in the test piece 10 on the side closest to the first edge 10a and the first edge 10a is d (mm). ), And the critical strain ε (%) is calculated from the above equation (1). The above measurement was performed on three molded test pieces, and the average value (%) of the critical strain ε was obtained.
The critical strain ε when the crack generation distance d at a thickness of 1.5 mm was 111 mm or more was set to “1.00 (%) or more”.

[Charpy impact strength]
The Charpy impact strength of the molded product of each example was measured according to JIS K7111-1.

[transparency]
The haze was measured for the molded product of each example in accordance with JIS K7361, and the case where the haze was 20% or less was defined as "transparent" and the case where the haze was more than 20% was defined as "opaque".

[Tensile strength]
The tensile strength of the alloy resin of each example was measured at a tensile speed of 50 mm / min according to JIS K7127.

[Experimental Example 1]
Melt flow of an alloy resin in which the ratio (W) of the mass of the MMA resin to the total mass of the PVC resin and the MMA resin is 0.3 or 0.5, and the PVC resin alone (ratio (W) = 0). The rate (R) was measured according to JIS K 7210 under the conditions of a load of 10 kg (98 N) and a temperature of 200 ° C. As the PVC-based resin, a PVC-based resin having a vinyl chloride unit ratio of 87% by mass and an average degree of polymerization of 700 was used. As the MMA-based resin, the product name "Acripet VH-001" manufactured by Mitsubishi Chemical Corporation (MMA unit ratio: 90% by mass, weight average molecular weight: 90,000, number average molecular weight: 50,000, MFR: 2. 0 g / 10 minutes) was used. FIG. 4 shows the results of plotting the melt flow rate (R) measured for each ratio (W) on a graph with the ratio (W) on the horizontal axis and the melt flow rate (R) on the vertical axis.
As shown in FIG. 4, the plot of the alloy resin having the ratio (W) of 0.3 and 0.5 was in the region A sandwiched between the straight line (1) and the straight line (2).

[Example 1]
70 parts by mass of PVC resin (ratio of vinyl chloride unit: 87% by mass, average degree of polymerization: 700) and MMA resin (trade name "Acrypet VH-001", manufactured by Mitsubishi Chemical Co., Ltd., MMA) as a molding material for the surface layer. Unit ratio: 90% by mass, weight average molecular weight: 90,000, number average molecular weight: 50,000, MFR: 2.0 g / 10 minutes) Using an alloy resin consisting of 30 parts by mass, the thickness is 1 by injection molding. A molded plate having a width of .5 mm, a width of 30 mm, and a length of 125 mm was produced. Next, 100 parts by mass of PVC resin (ratio of vinyl chloride unit: 87% by mass, average degree of polymerization: 700) and 5 mass of impact resistance improver W-300A (manufactured by Mitsubishi Chemical Co., Ltd.) as molding materials for the base material layer. A plate-shaped molded product having a thickness of 3.5 mm, a width of 30 mm, and a length of 125 mm having a surface layer on a base material layer by injection molding in which the molding plate is inserted into an injection molding mold using a material in which parts are mixed. Was produced.

[Example 2]
The mass ratio of the PVC resin and the MMA resin in the alloy resin, which is the molding material for the surface layer, was changed to 50:50, and the amount of the impact resistance improving agent W-300A used in the molding material for the base material layer was changed to 10 parts by mass. A molded product was produced in the same manner as in Example 1 except that it was changed to.

[Example 3]
70 parts by mass of PVC resin (ratio of vinyl chloride unit: 87% by mass, average degree of polymerization: 1000) and MMA resin (trade name "Acrypet VH-001", Mitsubishi Chemical) as alloy resin which is a molding material of the surface layer MMA unit ratio: 90% by mass, weight average molecular weight: 90,000, number average molecular weight: 50,000, MFR: 2.0 g / 10 minutes) 30 parts by mass) Using a material in which 100 parts by mass of a PVC resin (ratio of vinyl chloride units: 87% by mass, average degree of polymerization: 700) and 10 parts by mass of impact resistance improver W-300A (manufactured by Mitsubishi Chemical Co., Ltd.) are mixed. The molding material of the surface layer is extruded to a thickness of 1.0 mm by an auxiliary extruder, and the molding material of the base material layer is extruded by a main extruder to form two layers, cut to a length of 125 mm, and a thickness of 3.0 mm and a width. A plate-shaped molded product having a length of 30 mm and a length of 125 mm was produced.

[Example 4]
A molded product was produced in the same manner as in Example 2 except that the impact resistance improving agent W-300A of the base material layer was changed to 5 parts by mass.

[Example 5]
A molded product was produced in the same manner as in Example 3 except that the impact resistance improving agent W-300A for the base material layer was 5 parts by mass.

[Example 6]
The molding material of the base material layer was a mixture of 100 parts by mass of MMA resin (trade name "Acripet VH-001", manufactured by Mitsubishi Chemical Corporation) and 10 parts by mass of impact resistance improving agent W-300A (manufactured by Mitsubishi Chemical Corporation). A molded product was produced in the same manner as in Example 1 except that the material was changed.

[Comparative Example 1]
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 as the molding material of the surface layer was changed to 100: 0.

[Comparative 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 as the molding material of the surface layer was changed to 0: 100.

[Comparative Example 3]
A molded product was produced in the same manner as in Example 1 except that the impact resistance improving agent W-300A of the base material layer was set to 0 parts by mass.

[Comparative Example 4]
A molded product was produced in the same manner as in Comparative Example 3 except that the mass ratio of the PVC-based resin and the MMA-based resin as the molding material of the surface layer was changed to 30:70.

[Comparative Example 5]
A molded product was produced in the same manner as in Example 1 except that the amount of the impact resistance improving agent W-300A used in the molding material of the base material layer was changed to 25 parts by mass.

[Comparative Example 6]
70 parts by mass of PVC resin (ratio of vinyl chloride unit: 87% by mass, average degree of polymerization: 1000) and MMA resin (trade name "Acrypet VH-001", manufactured by Mitsubishi Chemical Co., Ltd., MMA) as a molding material for the surface layer. The unit ratio: 90% by mass, weight average molecular weight: 90,000, number average molecular weight: 50,000, MFR: 2.0 g / 10 minutes) using 30 parts by mass, an ABS resin (BS resin) as a molding material for the base material layer. Product name "Techno ABS600", manufactured by Techno Polymer Co., Ltd.) 100 parts by mass and impact resistance improver W-450A (manufactured by Mitsubishi Chemical Co., Ltd.) 5 parts by mass are mixed to form a surface layer molding material using a sub-extruder. Extruded to a thickness of 1.0 mm, extruded the molding material of the base material layer with a main extruder to form two layers, cut to a length of 125 mm, and made into a plate with a thickness of 3.0 mm, a width of 30 mm, and a length of 125 mm. A molded product was produced.

Table 1 shows the results of each example.

As shown in Table 1, the molded products of Examples 1 to 6 had solvent resistance, scratch resistance, impact resistance, and transparency. Among them, Examples 1, 3, 5, and 6 were particularly excellent in solvent resistance. Further, in Examples 1 to 3 and 6, the impact resistance was particularly excellent. Further, in Examples 1 to 3, 5 and 6, the scratch resistance was particularly excellent.

On the other hand, Comparative Example 1 in which the surface layer does not contain the MMA resin has solvent resistance and impact strength, but the pencil hardness is low and the scratch resistance is inferior. In Comparative Example 2 in which the surface layer did not contain a PVC resin, the pencil hardness was high, but the impact resistance and the solvent resistance were inferior. Comparative Examples 3 and 4 in which the base material layer did not contain the impact resistance improving agent had low impact resistance and were inferior. Comparative Example 4 was also inferior in solvent resistance. Comparative Example 5, which contains a large amount of impact resistance improving agent contained in the base material layer, was excellent in solvent resistance and impact strength, but had low pencil hardness and inferior transparency. Comparative Example 6 in which ABS resin was used as the base material layer had excellent solvent resistance, high pencil hardness, and excellent impact strength, but was not transparent.

1 ... Molded product, 2 ... Base material layer, 3 ... Surface layer, 10 ... Test piece, 20 ... Gauze, 30 ... Film, 100 ... Jig, 110 ... Curved surface.

Claims (5)

An alloy resin containing a vinyl chloride resin and a methyl methacrylate resin.
The mass ratio of the vinyl chloride resin to the methyl methacrylate resin is 20:80 to 90:10.
The ratio (W) of the mass of the methyl methacrylate-based resin to the total mass of the vinyl chloride-based resin and the methyl methacrylate-based resin and the melt flow rate (R) of the alloy resin measured according to JIS K 7210-1. When plotted on a graph with the ratio (W) on the horizontal axis and the melt flow rate (R) on the vertical axis, the plot is a straight line represented by the following equation (1) and the following equation (2). Alloy resin in the area sandwiched by the straight line represented by.
R = 6.25-4.7 × W ・ ・ ・ (1)
R = 4.50-4.7 × W ・ ・ ・ (2) The alloy resin according to claim 1, wherein the pencil hardness measured according to JIS K5600-5-4 is F or more. The alloy resin according to claim 1 or 2, wherein the critical strain ε measured in the solvent resistance test by the bending foam method is 0.45% or more. The alloy resin according to any one of claims 1 to 3, wherein the Charpy impact strength measured according to JIS K7111-1 is 5.0 kJ / m ^{2 or more.} A base material layer and a surface layer laminated on the base material layer are provided.
The surface layer contains the alloy resin according to any one of claims 1 to 4.
The base material layer contains a transparent resin and an impact resistance improving agent.
A molded product in which the content of the impact resistance improving agent in the base material layer is 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the transparent resin.

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