JP6938400B2 - Polyvinyl chloride resin composition with excellent yellowing resistance - Google Patents

Description

The present invention relates to a polyvinyl chloride resin composition having excellent yellowing resistance.

A paint containing an active energy ray-curable resin can be polymerized and cured in a short time by active energy rays such as ultraviolet rays and electron beams to form a coating film having excellent scratch resistance and other properties. It is often used for sheets, decorative films, and glass shatterproof films. On the other hand, since the active energy ray, particularly the electron beam, has a high energy, there is a problem that the film base material for forming the coating film turns yellow. Therefore, as a technique for solving the problem that the film substrate is discolored yellow by active energy rays, particularly electron beams, for example, Patent Documents 1 to 4 have been proposed. However, when the present inventor retested these, they were not sufficiently satisfactory.

Japanese Unexamined Patent Publication No. 2016-068524 Japanese Unexamined Patent Publication No. 2016-06598 Japanese Unexamined Patent Publication No. 2016-182819 Japanese Unexamined Patent Publication No. 2017-177496

An object of the present invention is to provide a polyvinyl chloride-based resin composition having excellent yellowing resistance (suppressing the problem of discoloration to yellow by active energy rays, particularly electron beams). A further object of the present invention is to provide a polyvinyl chloride-based resin composition having excellent yellowing resistance and transparency and suppressing troubles due to migration of a plasticizer.

As a result of diligent research, the present inventor has found that the above-mentioned problems can be achieved by a specific resin composition.

That is, the present invention
(A) 100 parts by mass of polyvinyl chloride resin;
(C) Polyester-based plasticizer 1 to 250 parts by mass;
Here, the mass average molecular weight of the above component (C) polyester-based plasticizer is 3100 or more;
For substrates for forming coatings with paints containing active energy raysetting resins;
It is a polyvinyl chloride resin composition.

The second invention is
(A) 100 parts by mass of polyvinyl chloride resin;
(B) Core shell rubber 1 to 100 parts by mass; and
(C) Polyester-based plasticizer 1 to 250 parts by mass;
Here, the mass average molecular weight of the above component (C) polyester-based plasticizer is 3100 or more;
For substrates for forming coatings with paints containing active energy raysetting resins;
It is a polyvinyl chloride resin composition.

The third invention is a molded product containing the polyvinyl chloride-based resin composition according to the first invention or the second invention.

The fourth invention is a film comprising the polyvinyl chloride-based resin composition according to the first invention or the second invention.

A fifth invention is a coating film formed by using a coating material containing an active energy ray-curable resin in order from the surface side, and a laminated film having a film layer according to the fourth invention.

The polyvinyl chloride-based resin composition of the present invention is excellent in yellowing resistance. The preferred polyvinyl chloride resin composition of the present invention is excellent in yellowing resistance and transparency, and troubles due to migration of the plasticizer are suppressed. Therefore, the molded product containing the polyvinyl chloride-based resin composition of the present invention can be suitably used as a base material for forming a coating film using a coating material containing an active energy ray-curable resin. Therefore, the film made of the polyvinyl chloride resin composition of the present invention is suitable as a film base material for forming a coating film on at least one surface of the film using a coating material containing an active energy ray-curable resin. Can be used.

In the present specification, the term "resin" is used as a term including a resin mixture containing two or more resins and a resin composition containing a component other than the resin. As used herein, the term "film" is used interchangeably or interchangeably with "sheet". Further, in the present specification, laminating a certain layer and another layer in order means directly laminating those layers and interposing one or more other layers such as an anchor coat between the layers. Includes both stacking. As used herein, the terms "film" and "sheet" are used for those that can be industrially rolled up. The term "board" is used for things that cannot be industrially rolled into rolls.

The term "greater than or equal to" related to a numerical range is used to mean a certain numerical value or a certain numerical value or more. For example, 20% or more means 20% or more than 20%. The term "less than or equal to" related to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%. Furthermore, the "~" symbol related to the numerical range is used to mean a certain numerical value, more than a certain numerical value and less than another certain numerical value, or another certain numerical value. Here, it is assumed that some other numerical value is larger than a certain numerical value. For example, 10-90% means 10%, greater than 10% and less than 90%, or 90%.

Except in the examples, or unless otherwise specified, all numbers used herein and in the claims should be understood as being modified by the term "about". Without attempting to limit the application of the doctrine of equivalents to the claims, each number should be interpreted in the light of significant figures and by applying conventional rounding techniques.

1. 1. Resin composition:
The polyvinyl chloride-based resin composition of the present invention contains (A) a polyvinyl chloride-based resin; and (C) a polyester-based plasticizer; The polyvinyl chloride-based resin composition of the present invention contains (A) polyvinyl chloride-based resin; (B) core-shell rubber; and (C) polyester-based plasticizer in one of preferred embodiments.

(A) Polyvinyl chloride resin:
The component (A) is a polyvinyl chloride resin. Examples of the polyvinyl chloride-based resin that can be used as the component (A) include polyvinyl chloride (vinyl chloride homopolymer); vinyl chloride / vinyl acetate copolymer, vinyl chloride / (meth) acrylic acid copolymer, and the like. Vinyl chloride / (meth) methyl acrylate copolymer, vinyl chloride / ethyl (meth) acrylate copolymer, vinyl chloride / maleic acid ester copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / propylene copolymer Combined, vinyl chloride / styrene copolymer, vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride ternary copolymer, vinyl chloride / styrene / acrylonitrile ternary Polymers, vinyl chloride / butadiene copolymers, vinyl chloride / isoprene copolymers, vinyl chloride / chlorinated propylene copolymers, vinyl chloride / vinylidene chloride / vinyl acetate ternary copolymers, vinyl chloride / acrylonitrile copolymers , Vinyl chloride-based copolymers of vinyl chloride such as vinyl chloride and various vinyl ether copolymers and other monomers copolymerizable with vinyl chloride; polyvinyl chloride-based copolymers such as post-chlorinated vinyl copolymers and vinyl chloride-based copolymers A modified (chlorinated, etc.) polymer; etc. can be mentioned. Further, a chlorinated polyolefin having a chemical structure similar to that of polyvinyl chloride, such as chlorinated polyethylene, may be used. Among these, polyvinyl chloride (vinyl chloride homopolymer) is preferable from the viewpoint of yellowing resistance. As the component (A), one kind or a mixture of two or more kinds of these can be used.

(B) Core shell rubber:
The component (B) is a core-shell rubber. The above component (B) functions to improve the film forming property of calendar roll rolling.

Examples of the component (B) include methacrylic acid ester / styrene / butadiene rubber graft copolymer, methacrylic acid ester / styrene / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, and acrylonitrile. -Styrene / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, acrylonitrile / styrene / acrylic acid ester rubber graft copolymer, methacrylic acid ester / acrylic acid ester rubber graft copolymer , Methacrylic acid ester / styrene / acrylic acid ester rubber graft copolymer, and methacrylate / acrylonitrile / acrylic acid ester rubber graft copolymer. Among these, from the viewpoint of yellowing resistance and weather resistance, acrylonitrile / styrene / acrylic acid ester rubber graft copolymer, methacrylic acid ester / acrylic acid ester rubber graft copolymer, methacrylic acid ester / styrene / acrylic acid ester Acrylic copolymer in which (meth) acrylic acid, acrylonitrile, styrene, etc. are graft-copolymerized on (meth) acrylic acid ester rubber, such as rubber graft copolymers and methacrylic acid ester / acrylonitrile / acrylic acid ester rubber graft copolymers. Core-shell rubber is preferred. As used herein, "(meth) acrylic acid" means acrylic acid or methacrylic acid. As the component (B), one kind or a mixture of two or more kinds of these can be used.

The blending amount of the above component (B) is not particularly limited because it is an optional component. The blending amount of the component (B) is usually 1 part by mass or more from the viewpoint of surely obtaining the effect of improving the film forming property of calendar roll rolling and the weather resistance with respect to 100 parts by mass of the component (A). It may be preferably 4 parts by mass or more, more preferably 7 parts by mass or more, and further preferably 10 parts by mass or more. On the other hand, from the viewpoint of transparency, it may be usually 100 parts by mass or less, preferably 60 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 20 parts by mass or less.

(C) Polyester-based plasticizer:
The component (C) is a polyester-based plasticizer. Examples of the component (C) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, and 1,4-butane as polyhydric alcohols. Using one or a mixture of two or more such as diol, 1,5-hexanediol, 1,6-hexanediol, and neopentyl glycol, oxalic acid, malonic acid, succinic acid, etc. are used as polyvalent carboxylic acids. Using one or a mixture of two or more such as glutaric acid, adipic acid, trimellitic acid, pimelli acid, oxalic acid, maleic acid, azelaic acid, sebatic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid. If desired, a polyester-based plasticizer using a monohydric alcohol, a monocarboxylic acid, or the like as a stopper can be mentioned. As the component (C), one kind or a mixture of two or more kinds of these can be used.

Polystyrene-equivalent obtained from a differential molecular weight distribution curve (hereinafter, may be abbreviated as "GPC curve") measured by gel permeation chromatography (hereinafter, may be abbreviated as "GPC") of the above component (C). The mass average molecular weight (Mw) is usually 3100 or more, preferably 3500 thousand or more, more preferably 4000 or more, still more preferably 4500 or more, most preferably, from the viewpoint of suppressing troubles due to migration of the plastic agent and from the viewpoint of yellowing resistance. It is preferably 5000 or more. From the viewpoint of suppressing troubles due to the migration of the plasticizer, a larger mass average molecular weight is preferable. On the other hand, from the viewpoint of the plasticization efficiency of the plasticizer, the mass average molecular weight may be usually 100,000 or less, preferably 50,000 or less, and more preferably 10,000 or less.

GPC measurement is a system that includes Tosoh Corporation's high performance liquid chromatography system "HLC-8320 (trade name)" (degasser, liquid feed pump, autosampler, column oven and RI (differential refractometer) detector. ) As a GPC column, two GPC columns "KF-806L (trade name)" from Shodex, and one each of "KF-802 (trade name)" and "KF-801 (trade name)". A total of 4 bottles were used by connecting them in the order of KF-806L, KF-806L, KF-802, and KF-801 from the upstream side; tetrahydrofuran for high performance liquid chromatography of Wako Pure Chemical Industries, Ltd. (without stabilizer). ) As the mobile phase; the flow rate is 1.0 ml / min, the column temperature is 40 ° C., the sample concentration is 1 mg / ml, and the sample injection amount is 100 microliters. The elution amount at each holding capacity can be obtained from the amount detected by the RI detector, assuming that the refractive index of the measurement sample does not depend on the molecular weight. The calibration curve from the retention capacity to the polystyrene-equivalent molecular weight is the standard polystyrene "EasiCal PS-1 (trade name)" (Plain A molecular weight 6375,000, 573000, 117000, 31500, 3480; Plane) manufactured by Agilent Technologies, Inc. It can be prepared using the molecular weight of B 2517,000, 270600, 71800, 10750, 705). As the analysis program, "TOSOH HLC-8320GPC EcoSEC (trade name)" manufactured by Tosoh Corporation can be used. For the theory of GPC and the actual measurement, refer to reference books such as "Size Exclusion Chromatography, High-Speed Liquid Chromatography of Polymers, Author: Sadao Mori, First Edition, 1st Edition, December 10, 1991". You can refer to it.

FIG. 1 shows a differential molecular weight distribution curve of the following component (C-1) used in the examples. It has a peak top of an oligomer component at molecular weights of 650, 860, 1100, and 1400, and a peak top of a main component at a molecular weight of 5500, and has a total mass average molecular weight of 5200 and a number average molecular weight of 2300.

The blending amount of the component (C) is usually 250 parts by mass or less, preferably 150 parts by mass, from the viewpoint of blocking resistance and suppressing troubles due to migration of the plasticizer with respect to 100 parts by mass of the component (A). Hereinafter, it may be more preferably 100 parts by mass or less, further preferably 60 parts by mass or less, still more preferably 45 parts by mass or less, and most preferably 35 parts by mass or less. On the other hand, the lower limit of the blending amount of the component (C) is usually 1 part by mass or more, preferably 5 parts by mass or more, and more preferably 10 parts by mass from the viewpoint of yellowing resistance, weather resistance, and calendar roll rolling film forming property. It may be 10 parts or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more.

It is preferable that the polyvinyl chloride-based resin composition of the present invention further contains a heat stabilizer usually used in the polyvinyl chloride-based resin composition. Examples of the heat stabilizer include organotin compounds, barium / zinc, calcium / zinc, and lead heat stabilizers. Among these, an organotin compound-based heat stabilizer is preferable from the viewpoint of yellowing resistance. Examples of the organic tin compound include dioctyl tin compounds such as dioctyl tin mercapto, dioctyl tin dilaurate, dioctyl tin versate, and dioctyl tin stearate; and dimethyl tin compounds such as dimethyl tin mercapto. can. As the heat stabilizer, one kind or a mixture of two or more kinds of these can be used. The blending amount of the heat stabilizer is usually 0.1 part by mass or more, preferably 0.5 part by mass or more, and more preferably 1 part by mass with respect to 100 parts by mass of the component (A) from the viewpoint of yellowing resistance. It may be more than one part. On the other hand, from the viewpoint of suppressing the bleed-out of the heat stabilizer, it may be usually 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less.

If desired, the polyvinyl chloride-based resin composition of the present invention may further contain other components other than the above components (A) to (C) to the extent that the object of the present invention is not violated. Examples of the other components include thermoplastic resins other than the above components (A) and (B); plasticizers other than the above component (C); antioxidants, weathering stabilizers, colorants, lubricants, and processing aids. Additives such as agents, nucleating agents, mold release agents, antistatic agents, urea-formaldehyde waxes, and surfactants;

Examples of the thermoplastic resin other than the above components (A) and (B) include poly (meth) acrylic acid ester, styrene / (meth) acrylic acid ester copolymer, ethylene / vinyl acetate copolymer; ethylene / ( Examples thereof include a meta) acrylate copolymer, an ethylene / methyl (meth) acrylate copolymer; and an ethylene / ethyl (meth) acrylate copolymer.

Examples of the plasticizer other than the above component (C) include a phthalic acid ester-based plasticizer, a trimellitic acid ester-based plasticizer, a pyromellitic acid ester-based plasticizer, an adipic acid ester-based plasticizer, and an itaconic acid ester-based plasticizer. , Citrate ester plasticizer, cyclohexanedicarboxylate plasticizer, epoxy plasticizer, trimellitic acid plasticizer, tetrahydrophthalic acid diester plasticizer, glycerin ester plasticizer, epoxy hexahydrophthalic acid diester plasticizer Agents, isosorbide diester plasticizers, phosphate plasticizers, azelaic acid plasticizers, sebatic acid plasticizers, stearic acid plasticizers, citric acid plasticizers, pyromellitic plasticizers, biphenyltetracarboxylics Examples thereof include acid ester-based plasticizers and chlorine-based plasticizers.

As the other component, one or more of these can be used.

The blending amount of the other components is not particularly limited because it is an optional component, but is usually about 10 parts by mass or less, or about 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A). good.

In the polyvinyl chloride-based resin composition of the present invention, the above-mentioned component (A), the above-mentioned component (C) and any component used as desired are melted simultaneously or in any order by using an arbitrary melt-kneader. It can be obtained by putting it in a kneading machine and melt-kneading it.

Examples of the melt kneader include batch kneaders such as pressure kneaders and mixers; extrusion kneaders such as single-screw extruders, co-rotating twin-screw extruders, and different-direction rotating twin-screw extruders; calendar roll kneaders, etc. Can be given. These may be used in any combination.

The obtained composition can be pelletized by any method and then molded into any molded product by any method. The pelletization can be carried out by a method such as hot cutting, strand cutting, and underwater cutting.

2. Mold:
The molded product of the present invention is a molded product containing the polyvinyl chloride-based resin composition of the present invention. The molded product of the present invention is a molded product, which is usually planned to form a coating film on a part or all of the surface of the molded product using a coating material containing an active energy ray-curable resin. .. The coating film-forming portion of the molded product of the present invention is usually composed of the polyvinyl chloride-based resin composition of the present invention. As such a molded body, for example, a composite molded body obtained by coextrusion molding using the polyvinyl chloride-based resin composition of the present invention as a skin material and an arbitrary thermoplastic resin as a core material; the present invention. A laminate of a film made of a polyvinyl chloride resin composition and a film, a sheet, or a plate made of an arbitrary thermoplastic resin; the laminate is subjected to thermal molding such as vacuum molding, pneumatic molding, and press molding. A method (film) in which a composite molded body obtained by shaping; and a film made of the polyvinyl chloride resin composition of the present invention are inserted into a mold as a skin material, and then an arbitrary thermoplastic resin is injected as a core material. A composite molded body obtained by (insert molding); and the like can be mentioned.

3. 3. the film:
The film of the present invention is a film made of the polyvinyl chloride-based resin composition of the present invention. The film of the present invention can be suitably used as a film base material for forming a coating film on one side or both sides of the film by using a coating material containing an active energy ray-curable resin.

The film of the present invention can be obtained by forming a film using an arbitrary film forming apparatus using the polyvinyl chloride-based resin composition of the present invention. Examples of the film film forming apparatus include a calender roll rolling processing machine and a calender roll rolling film forming apparatus including a take-up apparatus; and a T-die film forming apparatus including an extruder, a T die, and a take-up apparatus. ; And so on.

Examples of the calendar roll rolling machine include an upright type 3 roll, an upright type 4 roll, an L type 4 roll, an inverted L type 4 roll, and a Z type roll. Examples of the extruder include a single-screw extruder, a co-rotating twin-screw extruder, and a different-direction rotating twin-screw extruder. Examples of the T-die include a manifold die, a fishtail die, a coat hanger die, and the like.

The film of the present invention can be obtained by forming a film using the polyvinyl chloride-based resin composition of the present invention, preferably using a calendar roll rolling film forming apparatus. More preferably, it can be obtained by forming a film under the condition of a roll temperature of 160 ° C. to 200 ° C. using a calendar roll rolling film forming apparatus.

The thickness of the film of the present invention is not particularly limited, but may be usually 20 μm or more, preferably 50 μm or more from the viewpoint of handleability. On the other hand, from the viewpoint of meeting the demand for thinning of the article containing the film of the present invention, it may be usually 1000 μm or less, preferably 500 μm or less, and more preferably 200 μm or less.

The laminated film of the present invention is a laminated film containing one or more layers of the film of the present invention (a film made of the polyvinyl chloride-based resin composition of the present invention). The laminated film of the present invention usually has a coating film formed by using a coating material containing an active energy ray-curable resin and a layer of the film of the present invention in this order from the surface side.

Examples of the laminated film of the present invention include a coating film formed by using a coating film containing an active energy ray-curable resin in order from the surface side, and a laminated film having a layer of the film of the present invention. In the laminated film of such an aspect, the film of the present invention may be transparent, opaque, or colored. As used herein, the term "surface side" means the side of the surface that is normally visible in actual use. The "actual use state" means, for example, in the case of a decorative sheet, a state in which the decorative sheet is used for makeup and decoration on the surface of various articles.

The laminated film of the present invention has, for example, a coating film formed by using a coating material containing an active energy ray-curable resin, a layer of the film of the present invention, a printing layer, and a layer of a colored resin film in order from the surface side. Laminated film can be mentioned. Laminated films of this aspect can be used as decorative sheets, decorative films, and household appliances such as refrigerators, washing machines, air conditioners, mobile phones, and personal computers; furniture such as display shelves, storage bowls, cupboards, and desks; or floors. It can be suitably used for decorative makeup of building members such as walls and bathrooms. In the laminated film of such an aspect, the film of the present invention is preferably transparent. The total light transmittance of the film of the present invention (measured according to the 5.5.2 measurement method A of JIS K7105: 2011) is usually 60% or more, preferably 70% or more, more preferably 80% or more, still more preferably. It may be 85% or more, most preferably 90% or more. The higher the total light transmittance, the more preferable. The total light transmittance can be measured according to the 5.5.2 measurement method A of JIS K7105: 2011, for example, using a spectrophotometer "V-570 (trade name)" of JASCO Corporation.

FIG. 2 is a conceptual diagram of a cross section showing an example of a decorative sheet using the film of the present invention. From the surface side, the coating film 1 formed by using a paint containing an active energy ray-curable resin, the transparent film layer 2 of the present invention, the printing layer 3, and the colored thermoplastic resin film layer 4 are provided. doing. An adhesive layer or an adhesive layer may be formed directly or via an anchor coat on the surface of the colored thermoplastic resin film layer 4 opposite to the surface to be bonded to the printing layer 3.

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

Measurement method (a) Total light transmittance:
The measurement was performed using a spectrophotometer "V-570 (trade name)" of JASCO Corporation according to the 5.5.2 measurement method A of JIS K7105-2011.

(B) Yellowing resistance:
According to JIS Z8722: 2009, using the spectrophotometer "CM600d" of Konica Minolta Japan Co., Ltd., the XYZ coordinates are measured under the conditions including the geometric condition c and the component that becomes the mirror surface reflection, and the processing is performed by converting the coordinates. The previous L * a * b * coordinates were obtained. Subsequently, 50 KGy of γ-rays using cobalt-60 as a radiation source was irradiated. After irradiation, the sample was allowed to stand for 3 days under constant temperature and humidity conditions (temperature 23 ° C., relative humidity 50%). This is because the colored yellowing of the sample gradually progresses for a while after irradiation, so that the color is stabilized. The L * a * b * coordinates after processing were obtained according to the above method. The color difference (ΔE) is calculated from the L * a * b * coordinates before processing and the L * a * b * coordinates after processing using the calculation method (ΔE * ab (CIE1976)) built into the spectrophotometer. bottom. For the L * a * b * coordinates, you can refer to the homepage of Konita Minolta Japan Co., Ltd. (address below).
http://www.konicaminolta.jp/instruments/knowledge/color/part1/07.html

(C) Heat resistance:
After irradiation with 50 KGy of γ-rays using cobalt-60 as a radiation source, the sample was allowed to stand under constant temperature and humidity conditions (temperature 23 ° C., relative humidity 50%) for 3 days, and then according to JIS Z8722: 2009. Using the spectrocolorimeter "CM600d" of Konita Minolta Japan Co., Ltd., measure the XYZ coordinates under the conditions of geometric condition c and the condition including the component that becomes mirror reflection, and convert this to L * a before heat treatment. * B * Coordinates were calculated. Subsequently, it was treated in a gear oven at a temperature of 70 ° C. (humidity control was not performed) for 7 days, and further allowed to stand for 3 days under constant temperature and humidity conditions (temperature 23 ° C., relative humidity 50%). According to the above method, the L * a * b * coordinates after the heat resistance treatment were obtained. Color difference (ΔE) from the L * a * b * coordinates before the heat-resistant treatment and the L * a * b * coordinates after the heat-resistant treatment using the calculation method (ΔE * ab (CIE1976)) built in the spectrophotometer. Was calculated.

(D) Cold cycle:
After irradiation with 50 KGy of γ-rays using cobalt-60 as a radiation source, the sample was allowed to stand under constant temperature and humidity conditions (temperature 23 ° C., relative humidity 50%) for 3 days, and then according to JIS Z8722: 2009. Using the spectrocolorimeter "CM600d" of Konita Minolta Japan Co., Ltd., measure the XYZ coordinates under the conditions including geometric condition c and the component that becomes mirror reflection, and convert this to L * before the thermal cycle processing. The a * b * coordinates were obtained. Subsequently, a cold cycle treatment was carried out with a program in which the temperature was 50 ° C. and the relative humidity was 80% for 2 days, the temperature was 10 ° C. (humidity control was not performed) for 1 day, and the temperature was 50 ° C. and the relative humidity was 80% for 1 day. After that, the mixture was allowed to stand under constant temperature and humidity conditions (temperature 23 ° C., 50% relative humidity) for 3 days, and then the L * a * b * coordinates after the cooling / heating cycle were obtained according to the above method. Color difference (ΔE) from the L * a * b * coordinates before the cold cycle and the L * a * b * coordinates after the cold cycle using the calculation method built into the spectrophotometer (ΔE * ab (CIE1976)). Was calculated.

(E) Weather resistance:
After irradiation with 50 KGy of γ-rays using cobalt-60 as the radiation source, the sample was allowed to stand under constant temperature and humidity conditions (23 ° C., 50% relative humidity) for 3 days, and then Konita according to JIS Z8722: 2009. Using the spectrocolorimeter "CM600d" of Minolta Japan Co., Ltd., the XYZ coordinates are measured under the conditions including the geometric condition c and the component that becomes the mirror surface reflection, and by converting this, L * a * before the weather resistance treatment. The b * coordinates were calculated. ^{Subsequently, the irradiance 225 W / m 2} (trade name) of Suga Test Instruments Co., Ltd.'s sunshine carbon arc lamp type weather resistance tester (SWOM) "Sunshine Weather Meter S300 (trade name)" specified in JIS B7753: 2007 was used. The specifications of the glass filter are type A of the above standard table 2, the classification of irradiance is the normal type of the above standard table 3), water spray for 18 minutes every 120 minutes, atmospheric temperature 43 ° C, black panel temperature 63 ° C, and After treating for 2000 hours under the condition of relative humidity of 50 ± 5% and further standing for 3 days under the condition of constant temperature and humidity (temperature 23 ° C., 50% relative humidity), the weather-resistant treatment of L * was performed according to the above method. The a * b * coordinates were obtained. Color difference (ΔE) from the L * a * b * coordinates before the weather resistance treatment and the L * a * b * coordinates after the weather resistance treatment using the calculation method (ΔE * ab (CIE1976)) built into the spectrophotometer. Was calculated.

(To) Migration 1:
Using a mixture of 100 parts by mass of Denka's ABS resin "Denka ABS GR-2000 (trade name)" and 2 parts by mass of carbon black masterbatch (ABS resin base, 50% by mass of carbon), by injection molding method. A resin plate having a side of 15 cm and a thickness of 2 mm was obtained. Next, a sample (a film cut into a rectangle 8 cm in the machine direction and 6 cm in the horizontal direction) is placed in the center of the surface of the resin plate, and a stainless steel plate (rectangle 8 cm in length and 6 cm in width, thickness 2 mm) is further placed on the surface of the sample. ) Are stacked so that the sample and the stainless steel plate substantially match when viewed from above. Subsequently, a 1 kg weight was placed in the center of the surface of the stainless steel plate, and the treatment was carried out in a gear oven at a temperature of 70 ° C. (humidity control was not performed) for 7 days. The contact points of the resin plate with the sample after the treatment were visually observed and evaluated according to the following criteria. FIG. 3 shows a photograph of the treated resin plate (D evaluation) of Example 5.
A: No change is observed at the contact point.
B: A slight discoloration is observed when the contacted portion and the non-contacted portion are compared. However, there is no part that has lost its luster.
C: The contact portion was discolored and a portion having lost the glossiness was generated.
D: The contact portion was significantly discolored and lost a glossy feeling in a wide range. It became marbling.

(G) Migration 2:
Except that the polystyrene "Toyo Styrene HI H450 (trade name)" of Toyo Styrene Co., Ltd. was used instead of the ABS resin, the same procedure as in (to) Transferability 1 was performed.

Raw materials used (A) Polychlorinated resin:
(A-1) A polyvinyl chloride homopolymer having a degree of polymerization of 800.

(B) Core shell rubber:
(B-1) Mitsubishi Chemical Corporation's core shell rubber (methyl methacrylate / styrene / ethyl acrylate rubber graft copolymer) "Metabrene W-300A (trade name)"

(C) Polyester-based plasticizer:
(C-1) ADEKA Corporation's polyester-based plasticizer "ADEKA Sizer PN-280 (trade name)". Mass average molecular weight (Mw) 5200.
(C-2) ADEKA Corporation's polyester-based plasticizer "ADEKA Sizer PN-446 (trade name)". Mass average molecular weight (Mw) 5300.
(C-3) DIC Corporation's polyester-based plasticizer "Polysizer W-4010 (trade name)". Mass average molecular weight (Mw) 10000.

(C'-1) ADEKA Corporation's polyester-based plasticizer "ADEKA Sizer PN-7160 (trade name)". Mass average molecular weight (Mw) 1200.
(C'-2) Bis phthalate (2-ethylhexyl).

(D) Optional component:
(D-1) ADEKA Corporation's dioctyl tin mercapto-based stabilizer "ADEKA STAB 465 (trade name)".
(D-2) ADEKA Corporation's lubricant "ADEKA STAB LS-16 (trade name)".

Examples 1-7
The resin composition having the composition (part by mass) shown in Table 1 was melt-kneaded using a mixer kneader under the condition of a resin temperature of 140 ° C. at the time of discharge to obtain a polyvinyl chloride-based resin composition. Next, using a film-forming device equipped with an inverted L-shaped 4-roll calendar roll rolling machine and a take-up device of Nippon Roll Manufacturing Co., Ltd., the first roll temperature was 180 ° C, the second roll temperature was 180 ° C, and the third roll was 185. A film having a thickness of 80 μm was formed under the conditions of ° C., a fourth roll of 180 ° C., and a take-up speed of 60 m / min. The above tests (a) to (g) were performed. The results are shown in Table 1.

The polyvinyl chloride-based resin composition of the present invention is excellent in yellowing resistance and transparency, and troubles due to migration of a plasticizer are suppressed. The results of heat resistance, cold cycle, and weather resistance tests performed after γ-ray irradiation are also good.

It is a differential molecular weight distribution curve of the said component (C-1) used in an Example. It is a conceptual diagram of the cross section which shows an example of the decorative sheet using the film of this invention. It is a photograph of the above-mentioned (to) transferability 1 test result (processed resin plate (D evaluation)) of Example 5.

1: Coating film formed using a paint containing an active energy ray-curable resin 2: Transparent film layer of the present invention 3: Printing layer 4: Colored thermoplastic resin film layer

Claims (8)

(A) 100 parts by mass of polyvinyl chloride resin;
(C) Polyester-based plasticizer 1 to 250 parts by mass;
Here, the mass average molecular weight of the above component (C) polyester-based plasticizer is 3100 or more;
For substrates for forming coatings with paints containing active energy raysetting resins;
Polyvinyl chloride resin composition.
(A) 100 parts by mass of polyvinyl chloride resin;
(B) Core shell rubber 1 to 100 parts by mass; and
(C) Polyester-based plasticizer 1 to 250 parts by mass;
Here, the mass average molecular weight of the above component (C) polyester-based plasticizer is 3100 or more;
For substrates for forming coatings with paints containing active energy raysetting resins;
Polyvinyl chloride resin composition.
A polyvinyl chloride-based resin composition for a base material for forming a coating film using the paint containing the active energy ray-curable resin according to claim 2, wherein the core-shell rubber of the component (B) contains an acrylic core-shell rubber. ..
The active energy ray curing according to any one of claims 1 to 3, further comprising a heat stabilizer of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin of the component (A). A polyvinyl chloride-based resin composition for a base material for forming a coating film using a paint containing a sex resin.
A molded body for a base material for forming a coating film using a coating material containing an active energy ray-curable resin, which comprises the polyvinyl chloride-based resin composition according to any one of claims 1 to 4.
A film for a base material for forming a coating film using a coating material containing an active energy ray-curable resin, which comprises the polyvinyl chloride-based resin composition according to any one of claims 1 to 4 .
A coating film formed using a paint containing an active energy ray-curable resin in order from the surface side,
A laminated film having a layer of the film according to claim 6.
A decorative sheet containing the laminated film according to claim 7.

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