JP7220700B2 - Thermoplastic resin composition with excellent yellowing resistance - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent yellowing resistance. Furthermore, the present invention provides a film substrate suitable for a molded article or film formed from a thermoplastic resin composition excellent in yellowing resistance, particularly a coating film formed from a paint containing an active energy ray-curable resin. Regarding.

A paint containing an active energy ray-curable resin can be polymerized and cured in a short time by an active energy ray such as an ultraviolet ray or an electron beam to form a coating film having excellent properties such as scratch resistance. Therefore, paints containing active energy ray-curable resins are frequently used for decorative sheets, decorative films, anti-scattering films for glass, and the like. On the other hand, since active energy rays, especially electron rays, have high energy, there is a problem that the film substrate for forming the coating film is discolored yellow. Therefore, for example, Patent Documents 1 to 4 have proposed techniques for solving the problem that the film substrate is discolored yellow by active energy rays, particularly electron rays. However, when the inventor of the present invention repeated these experiments, they were not fully satisfactory.

JP 2016-068524 A JP 2016-069598 A JP 2016-182819 A JP 2017-177496 A

An object of the present invention is to provide a thermoplastic resin composition that is excellent in yellowing resistance (in which the problem of yellow discoloration due to active energy rays, particularly electron rays is suppressed).
A further object of the present invention is to provide a thermoplastic resin composition which is preferably excellent in yellowing resistance and transparency, and in which troubles due to migration of a plasticizer are suppressed.

As a result of intensive research, the inventors of the present invention have found that the above objects can be achieved with a specific paint.

That is, aspects of the present invention are as follows.
[1].
A thermoplastic resin composition for a substrate of a coating film formed from a coating containing an active energy ray-curable resin,
(A) 1 to 100% by mass of amorphous or low-crystalline polyester resin; and (B) 99 to 0% by mass of polyvinyl chloride resin
100 parts by mass of a resin mixture in which the sum of the component (A) amorphous or low-crystalline polyester resin and the component (B) polyvinyl chloride resin is 100% by mass; and (C) A thermoplastic resin composition containing 1 to 100 parts by mass of core-shell rubber.
[2].
A thermoplastic resin composition for a substrate of a coating film formed from a coating containing an active energy ray-curable resin,
(A) 1 to 99% by mass of amorphous or low-crystalline polyester resin; and (B) 99 to 1% by mass of polyvinyl chloride resin
100 parts by mass of a resin mixture in which the sum of the component (A) amorphous or low-crystalline polyester resin and the component (B) polyvinyl chloride resin is 100% by mass; and (C) including 1 to 100 parts by mass of core-shell rubber,
Furthermore, with respect to 100 parts by mass of the component (B) polyvinyl chloride resin,
(D) A resin composition containing 1 to 250 parts by mass of a polyester plasticizer.
[3].
The thermoplastic resin composition according to item [2] above, wherein the weight average molecular weight of the component (D) polyester plasticizer is 3,100 or more.
[4].
A molded article formed from the thermoplastic resin composition according to any one of [1] to [3] above.
[5].
A film formed from the thermoplastic resin composition according to any one of [1] to [3] above.
[6].
From the surface side,
A laminated film comprising a coating film formed from a paint containing an active energy ray-curable resin, and a layer of the film according to item [5] above as a substrate.

The thermoplastic resin composition of the present invention is excellent in yellowing resistance. The thermoplastic resin composition of the preferred embodiment of the present invention is excellent in yellowing resistance and transparency, and troubles due to migration of the plasticizer are suppressed. Therefore, the molded article formed from the thermoplastic resin composition of the present invention can be suitably used as a substrate for a coating film formed from a coating containing an active energy ray-curable resin. Furthermore, the film of the thermoplastic resin composition of the present invention is preferably used as a film substrate for forming a coating film on at least one surface thereof using a coating material containing an active energy ray-curable resin. can be done.

1 is a differential molecular weight distribution curve of the following component (D-1) used in Examples. 1 is a schematic cross-sectional view showing an example of a decorative sheet using the film of the present invention; FIG. It is a photograph showing an example in the case of D evaluation of (vi) migration test 1 in Examples described later.

As used herein, the term "resin" includes resin mixtures containing two or more resins and resin compositions containing components other than resins. The term "film" is used herein interchangeably or interchangeably with "sheet." Further, in this specification, laminating a certain layer and another layer in order means directly laminating those layers, and interposing one or more layers such as an anchor coat between those layers. and lamination. As used herein, the terms "film" and "sheet" are used for those that can be industrially wound into rolls. The term "plate" is used for those that cannot be industrially wound into rolls.

The term "greater than or equal to" regarding a numerical range is used to mean a certain numerical value or greater than a certain numerical value. For example, 20% or more means 20% or more than 20%. The term "up to" relating 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 “~” relating to numerical ranges is used to mean a certain numerical value, greater than a certain numerical value and less than another numerical value, or some other numerical value. Here, another certain numerical value is assumed to be a larger numerical value than the 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 numerical values used in the specification and claims are to be understood as being modified by the term "about." Without trying to limit the application of the doctrine of equivalents to the claims, each numerical value should be interpreted in the light of significant digits and by applying conventional rounding techniques.

1. Thermoplastic Resin Composition The thermoplastic resin composition of the present invention contains (A) an amorphous or low-crystalline polyester resin; and (C) a core-shell rubber. In one preferred embodiment, the thermoplastic resin composition of the present invention contains (A) an amorphous or low-crystalline polyester-based resin; (B) a polyvinyl chloride-based resin; and (C) a core-shell rubber. In another preferred embodiment, the thermoplastic resin composition of the present invention comprises (A) an amorphous or low-crystalline polyester resin; (B) a polyvinyl chloride resin; (C) a core-shell rubber; (D) Contains a polyester plasticizer.

(A) Amorphous or low-crystalline polyester resin The amorphous or low-crystalline polyester resin of component (A) has high transparency and gloss, and is excellent in embossability and impact resistance. It has the feature of It also has excellent miscibility with the above components (B) to (D). The above component (A) is preferably an amorphous polyester resin. The above component (A) is more preferably an amorphous aromatic polyester resin.

In this specification, a differential scanning calorimeter is used, after holding at 320 ° C. for 5 minutes, cooling to -50 ° C. at a temperature decrease rate of 20 ° C./min, holding at -50 ° C. for 5 minutes, 20 ° C./ Polyester with a heat of fusion of 5 J / g or less in the curve of the last heating process (second melting curve) measured by a program of heating to 320 ° C. at a heating rate of 1 minute; Low crystallinity is defined as a polyester having a viscosity of 60 J/g or less, preferably 40 J/g or less, more preferably 20 J/g or less, still more preferably 15 J/g or less, and most preferably 12 J/g or less. As the differential scanning calorimeter, for example, a Diamond DSC differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd. can be used.

The amorphous or low-crystalline polyester resin is not particularly limited as long as it has amorphous or low-crystallinity. Copolymers of acids and polyols such as aliphatic polyols and aromatic polyols can be mentioned.

In the present specification, structural units derived from a polycarboxylic acid mainly include structural units derived from an aromatic polycarboxylic acid (usually 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more) is defined as an aromatic polyester.

Examples of the aromatic polycarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid; and ester-forming derivatives thereof. Examples of the aliphatic polycarboxylic acids include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, and hexadecanedicarboxylic acid. linear aliphatic dicarboxylic acids such as acids, octadecanedicarboxylic acid, and eicosanedicarboxylic acid; 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, and alicyclic dicarboxylic acids such as norbornane dicarboxylic acid; and ester-forming derivatives thereof. One or a mixture of two or more thereof can be used as the polycarboxylic acid.

Examples of the aliphatic polyhydric ol include ethylene glycol, diethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3- methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and spiroglycol aliphatic diols such as (3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane); and ester-forming properties thereof Derivatives etc. can be mentioned.
Examples of the aromatic polyols include xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, bisphenol A, bisphenol A aromatic polyols such as alkylene oxide adducts of; and ester-forming derivatives thereof. As the above polyhydric ol, one or a mixture of two or more thereof can be used.

As the amorphous or low-crystalline polyester resin, for example, the total sum of structural units derived from polyvalent carboxylic acid is 100 mol%, and the total sum of structural units derived from polyol is 100 mol%. As (1) 90 to 100 mol% of structural units derived from terephthalic acid, and (2) 60 to 80 mol% of structural units derived from ethylene glycol, and 20 to 40 mol% of structural units derived from 1,4-cyclohexanedimethanol. mol %, and 0 to 10 mol % of structural units derived from diethylene glycol; (1) 90 to 100 mol % of structural units derived from terephthalic acid, and (2) derived from ethylene glycol. 20-60 mol %, typically 32-42 mol % of structural units derived from 1,4-cyclohexanedimethanol, 40-80 mol %, typically 58-68 mol % of structural units derived from diethylene glycol (1) 50 to 99 mol% of structural units derived from terephthalic acid and 1 to 50 mol% of structural units derived from isophthalic acid, and ( 2) acid-modified polycyclohexylene dimethylene terephthalate (PCTA) containing 90 to 100 mol% of structural units derived from 1,4-cyclohexanedimethanol; (1) 90 to 100 mol% of structural units derived from terephthalic acid, and 0 to 10 mol % of structural units derived from isophthalic acid, and (2) 50 to 90 mol % of structural units derived from 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3 - a copolymer containing 10 to 50 mol% of structural units derived from cyclobutanediol; (1) 60 to 90 mol% of structural units derived from terephthalic acid and 10 to 40 mol% of structural units derived from isophthalic acid, and (2) 70 to 96 mol% of structural units derived from ethylene glycol, 4 to 30 mol% of structural units derived from neopentyl glycol, less than 1 mol% of structural units derived from diethylene glycol, and 1 structural unit derived from bisphenol A Acid-modified and glycol-modified polyethylene terephthalate containing less than mol % can be mentioned.

As the amorphous or low-crystalline polyester resin, one or a mixture of two or more thereof can be used.

The glass transition temperature of the amorphous or low-crystalline polyester resin is usually 50 to 140° C., preferably 60 to 120° C., more preferably 60 to 120° C., from the viewpoint of yellowing resistance and miscibility with the component (B). may be from 70 to 110°C, more preferably from 75 to 105°C.

In this specification, the glass transition temperature is measured according to JIS K7121-1987 using a differential scanning calorimeter, held at 250 ° C. for 3 minutes, cooled at 10 ° C./min to 20 ° C., held at 20 ° C. for 3 minutes, It is the midpoint glass transition temperature calculated from the curve of the last heating process measured with a program of heating up to 250°C at 10°C/min. As the differential scanning calorimeter, for example, a Diamond DSC differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd. can be used.

(B) Polyvinyl chloride resin Polyvinyl chloride resin that can be used as the above component (B) is not particularly limited, but examples include polyvinyl chloride (vinyl chloride homopolymer); vinyl chloride/vinyl acetate copolymer. , vinyl chloride/(meth)acrylic acid copolymer, vinyl chloride/methyl (meth)acrylate copolymer, vinyl chloride/ethyl (meth)acrylate copolymer, vinyl chloride/maleate ester copolymer, chloride Vinyl/ethylene copolymer, vinyl chloride/propylene copolymer, vinyl chloride/styrene copolymer, vinyl chloride/isobutylene copolymer, vinyl chloride/vinylidene chloride copolymer, vinyl chloride/styrene/maleic anhydride ternary Copolymer, vinyl chloride/styrene/acrylonitrile terpolymer, vinyl chloride/butadiene copolymer, vinyl chloride/isoprene copolymer, vinyl chloride/chlorinated propylene copolymer, vinyl chloride/vinylidene chloride/vinyl acetate Vinyl chloride-based copolymers of vinyl chloride and other monomers copolymerizable with vinyl chloride, such as terpolymers, vinyl chloride/acrylonitrile copolymers, vinyl chloride/various vinyl ether copolymers; post-chlorinated vinyl Modified (eg, chlorinated) polyvinyl chloride and vinyl chloride copolymers such as copolymers can be mentioned. Furthermore, chlorinated polyolefins similar in chemical structure to 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 polyvinyl chloride resin of component (B), one or a mixture of two or more of these can be used.

The blending ratio of the amorphous or low-crystalline polyester resin of component (A) and the polyvinyl chloride resin of component (B) in the thermoplastic resin composition of the present invention is is used) The sum of the component (A) and the component (B) is 100% by mass, and from the viewpoint of yellowing resistance, the component (A) is usually 1% by mass or more (the component (B) 99 % by mass or less), preferably 20% by mass or more (80% by mass or less of component (B)), more preferably 40% by mass or more (60% by mass or less of component (B)), still more preferably 60% by mass or more ( 40% by mass or less of component (B), most preferably 80 to 100% by mass (20 to 0% by mass of component (B)). On the other hand, the mixing ratio of the amorphous or low-crystalline polyester resin of component (A) and the polyvinyl chloride resin of component (B) is The above component (A) is usually 99% by mass or less (the above component (B) is 1% by mass or more), preferably 90% by mass or less (the above component (B) is 10% by mass or more), more preferably 70% by mass or less (the above component (B) 30% by mass or more), more preferably 50% by mass or less (above 50% by mass of component (B)), most preferably 1 to 30% by mass (above 99 to 70% by mass of component (B)) can be

(C) Core-shell rubber The core-shell rubber of component (C) functions to improve the film formability of the resin composition by calendar roll rolling.

The core-shell rubber of component (C) is not particularly limited. Butadiene rubber graft copolymer, acrylonitrile-styrene/styrene-butadiene rubber graft copolymer, acrylonitrile-styrene/ethylene-propylene rubber graft copolymer, acrylonitrile-styrene/acrylate rubber graft copolymer, methacrylate/ Acrylic acid ester rubber graft copolymers, methacrylic acid ester/styrene/acrylic acid ester rubber graft copolymers, and methacrylic acid ester/acrylonitrile/acrylic acid ester rubber graft copolymers may be mentioned. Among them, acrylonitrile/styrene/acrylate rubber graft copolymer, methacrylate/acrylate rubber graft copolymer, methacrylate/styrene/acrylate ester rubber graft copolymer, and methacrylate/styrene/acrylate ester rubber graft copolymer Rubber graft copolymers, acrylic ester rubber graft copolymers such as methacrylic acid ester/acrylonitrile/acrylic acid ester rubber graft copolymers, etc., in which (meth)acrylic acid, acrylonitrile, styrene, etc. are graft copolymerized. Core-shell rubber is preferred. As used herein, "(meth)acrylic acid" means acrylic acid or methacrylic acid. As the core-shell rubber of component (C), one or a mixture of two or more thereof can be used.

The content of the core-shell rubber of component (C) is usually 1 mass based on the sum of component (A) and component (B) being 100 parts by mass, from the viewpoint of weather resistance and calendar roll rolling film formability. parts or more, preferably 4 parts by mass or more, more preferably 7 parts by mass or more, and even more preferably 10 parts by mass or more. On the other hand, from the viewpoint of transparency, the content of the core-shell rubber of component (C) is usually 100 parts by mass or less, preferably 60 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 20 parts by mass or less. It's okay.
In one embodiment, the amount of the core-shell rubber of component (C) is usually 1 part by mass or more and 100 parts by mass or less, with the sum of component (A) and component (B) being 100 parts by mass, preferably 1-60 parts by mass, 1-40 parts by mass, 1-20 parts by mass, 4-100 parts by mass, 4-60 parts by mass, 4-40 parts by mass 4 parts to 20 parts by mass, 7 to 100 parts by mass, 7 to 60 parts by mass, 7 to 40 parts by mass, 7 to 20 parts by mass, 10 It may be from 10 parts by mass to 60 parts by mass, from 10 parts by mass to 40 parts by mass, or from 10 parts by mass to 20 parts by mass.

(D) Polyester plasticizer The polyester plasticizer of component (D) is not particularly limited, but examples include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1, One or a mixture of two or more of 3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, and neopentyl glycol Polycarboxylic acids used include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, trimellitic acid, pimelic acid, suberic acid, maleic acid, azelaic acid, sebacic acid, fumaric acid, phthalic acid, and isophthalic acid. , and terephthalic acid, or a mixture of two or more thereof, optionally using a monohydric alcohol, monocarboxylic acid or the like as a stopper. As the polyester plasticizer of component (D), one or a mixture of two or more thereof can be used.

From the differential molecular weight distribution curve (hereinafter sometimes abbreviated as "GPC curve") measured by gel permeation chromatography (hereinafter sometimes abbreviated as "GPC") of the polyester plasticizer of component (D) The obtained polystyrene-equivalent mass average molecular weight (Mw) is usually 3,100 or more, preferably 3,500,000 or more, more preferably 4,000 or more, and still more preferably, from the viewpoint of suppressing troubles due to migration of the plasticizer and from the viewpoint of yellowing resistance. may be 4500 or more, most preferably 5000 or more. From the viewpoint of preventing troubles due to migration of the plasticizer, the larger the weight average molecular weight, the better. 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, more preferably 10,000 or less.
In one aspect, the weight average molecular weight of the polyester plasticizer of component (D) is usually 3,100 or more and 100,000 or less, preferably 3,100 or more and 50,000 or less, 3,100 or more and 10,000 or less, 3,500,000 or more and 100,000 or less, preferably is 3,500 to 50,000, 3,500 to 10,000, 4,000,000 to 100,000, preferably 4,000 to 50,000, 4,000 to 10,000, 4,500,000 to 100,000, preferably 4,500 to 50,000 4,500 to 10,000, 5,000,000 to 100,000, preferably 5,000 to 50,000, or 5,000 to 10,000.

GPC measurement was performed using a high-performance liquid chromatography system "HLC-8320" (trade name) manufactured by Tosoh Corporation (a system including a degasser, a liquid pump, an autosampler, a column oven and an RI (differential refractive index) detector). As GPC columns, two Shodex GPC columns "KF-806L" (trade name), one each of "KF-802" (trade name) and "KF-801" (trade name), total 4 KF-806L, KF-806L, KF-802, and KF-801 are connected in this order from the upstream side and used; As the mobile phase, the conditions are flow rate of 1.0 ml/min, column temperature of 40° C., sample concentration of 1 mg/ml, and sample injection volume of 100 microliters. The amount of elution in each retention volume can be obtained from the amount detected by the RI detector, assuming that the refractive index of the sample to be measured does not depend on the molecular weight. In addition, the calibration curve from the retention volume to the polystyrene equivalent molecular weight was obtained using the standard polystyrene "EasiCal PS-1" (trade name) of Agilent Technology Co., Ltd. B with molecular weights of 2517000, 270600, 71800, 10750, 705). As an analysis program, Tosoh Corporation's "TOSOH HLC-8320GPC EcoSEC" (trade name) can be used. For the theory and measurement of GPC, reference books such as "Size Exclusion Chromatography, High Performance Liquid Chromatography of Polymers, Author: Sadao Mori, First Edition, First Edition, December 10, 1991" by Kyoritsu Shuppan Co., Ltd. can be referred to.
The mass-average molecular weight of the polyester plasticizer used in the examples described later can also be obtained by this method.

FIG. 1 shows the differential molecular weight distribution curve of the following component (D-1) used in Examples. It has oligomer component peak tops at molecular weights of 650, 860, 1100 and 1400, and major component peak tops at molecular weight 5500, and the overall mass average molecular weight is 5200 and the number average molecular weight is 2300.

The amount of the polyester-based plasticizer of the component (D) is usually 250 parts by mass or less per 100 parts by mass of the component (B), from the viewpoint of blocking resistance and prevention of problems due to migration of the plasticizer. It may be preferably 150 parts by mass or less, more preferably 100 parts by mass or less, even more 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 polyester plasticizer of component (D) is usually 1 part by mass or more, preferably 5 parts by mass or more, from the viewpoint of yellowing resistance, weather resistance, and calendar roll rolling film formability. More preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and most preferably 20 parts by mass or more.
In one aspect, the amount of the polyester plasticizer of component (D) is usually 1 part by mass or more and 250 parts by mass or less, preferably 1 part by mass or more and 150 parts by mass, relative to 100 parts by mass of component (B). parts or less, 1 to 100 parts by mass, 1 to 60 parts by mass, 1 to 45 parts by mass, 1 to 35 parts by mass, 5 to 250 parts by mass, 5 parts by mass 5 to 100 parts by mass, 5 to 60 parts by mass, 5 to 45 parts by mass, 5 to 35 parts by mass, 10 to 250 parts by mass 10 to 150 parts by mass, 10 to 100 parts by mass, 10 to 60 parts by mass, 10 to 45 parts by mass, 10 to 35 parts by mass, 15 parts by mass 15 to 150 parts by mass, 15 to 100 parts by mass, 15 to 60 parts by mass, 15 to 45 parts by mass, 15 to 35 parts by mass , 20 to 250 parts by mass, 20 to 150 parts by mass, 20 to 100 parts by mass, 20 to 60 parts by mass, 20 to 45 parts by mass, or 20 parts by mass It may be more than or equal to 35 parts by mass or less.

The thermoplastic resin composition of the present invention preferably further contains a heat stabilizer. Examples of the heat stabilizer include, but are not limited to, organotin compound-based, barium/zinc-based, calcium/zinc-based, and lead-based heat stabilizers. Among these, organotin compound-based heat stabilizers are preferred from the viewpoint of yellowing resistance. Examples of the organic tin compounds include dioctyltin compounds such as dioctyltin mercapto, dioctyltin dilaurate, dioctyltin versatate, and dioctyltin stearate; and dimethyltin compounds such as dimethyltin mercapto. . One or a mixture of two or more thereof can be used as the heat stabilizer. The amount of the heat stabilizer compounded is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass, based on 100 parts by mass of the component (B), from the viewpoint of yellowing resistance. It may be more than part. On the other hand, from the viewpoint of suppressing bleed-out of the 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.
In one aspect, the amount of the heat stabilizer to be blended is usually 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.1 parts by mass or more and 7 parts by mass or less per 100 parts by mass of the component (B). , 0.1 to 5 parts by mass, 0.5 to 10 parts by mass, 0.5 to 7 parts by mass, 0.5 to 5 parts by mass, 1 to 10 parts by mass It may be 1 part by mass or more and 7 parts by mass or less, or 1 part by mass or more and 5 parts by mass or less.

If desired, the thermoplastic resin composition of the present invention may further contain components other than the components (A) to (D) as long as the objects of the present invention are not compromised. Examples of the other components include thermoplastic resins other than the components (A) to (C); plasticizers other than the component (D); antioxidants, weather stabilizers, colorants, lubricants, and processing aids. agents, nucleating agents, release agents, antistatic agents, and additives such as surfactants.

Thermoplastic resins other than the above components (A) to (C) include, for example, poly(meth)acrylate, styrene/(meth)acrylate copolymer, ethylene/vinyl acetate copolymer, ethylene/( A meth)acrylic acid copolymer, an ethylene/methyl (meth)acrylate copolymer, an ethylene/ethyl (meth)acrylate copolymer, and the like can be mentioned.

Examples of plasticizers other than the component (D) include phthalate plasticizers, trimellitate plasticizers, pyromellitic ester plasticizers, adipate plasticizers, and itaconate plasticizers. , citric acid ester plasticizer, cyclohexanedicarboxylate plasticizer, epoxy plasticizer, trimellitic acid plasticizer, tetrahydrophthalate diester plasticizer, glycerin ester plasticizer, epoxy hexahydrophthalate diester plasticizer plasticizer, isosorbide diester plasticizer, phosphate plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, pyromellitic acid plasticizer, biphenyltetracarboxylic acid Ester-based plasticizers, chlorine-based plasticizers, and the like can be mentioned.

One or more of these can be used as the other components.

The blending amount of the above-mentioned other components is not particularly limited because they are optional components. It may be usually about 10 parts by mass or less, or about 0.01 to 10 parts by mass, per 100 parts by mass of the component (A), the component (B), and the component (C).

The thermoplastic resin composition of the present invention is prepared by melt-kneading the component (A), the component (C), and optional optional components simultaneously or in any order using any melt-kneader. It can be obtained by putting it into a machine and melt-kneading it.

Examples of the melt-kneader include batch kneaders such as pressure kneaders and mixers; extrusion kneaders such as a single-screw extruder, a co-rotating twin-screw extruder, and a counter-rotating twin-screw extruder; calendar roll kneaders and the like. can be mentioned. Any combination of these may be used.

The resulting composition can be pelletized by any method and then molded into any molded article by any method. The pelletization can be carried out by methods such as hot cutting, strand cutting, and underwater cutting.

2. Molded Article The molded article of the present invention is a molded article formed from the thermoplastic resin composition of the present invention. The expression "formed from the thermoplastic resin composition" in relation to the "molded article" here means that the thermoplastic resin composition is used as part or all of the raw material for the molded article. This can be rephrased as a molded article partially or entirely containing the cured product of the thermoplastic resin composition of the present invention. Its shape is not particularly limited and can be arbitrarily designed.
The molded article of the present invention is usually a molded article intended to form a coating film on part or all of the surface of the molded article using a paint containing an active energy ray-curable resin. . The coating film-forming portion of the molded article of the present invention is usually composed of the thermoplastic resin composition of the present invention.
The shape and configuration of such a molded body are not particularly limited. Composite molded article obtained; A laminate of a film formed from the thermoplastic resin composition of the present invention and a film, sheet, or plate formed from an arbitrary thermoplastic resin; , and a composite molded article obtained by shaping by thermoforming such as press molding; and after inserting the film formed from the thermoplastic resin composition of the present invention into the mold as a skin material, any thermoplastic A composite molding obtained by a method of injecting a resin as a core material (film insert molding) can be mentioned.

3. Film The film of the present invention is a film formed from the thermoplastic resin composition of the present invention. The film of the present invention can be suitably used as a film substrate for forming a coating film on one or both sides of the film using a coating containing an active energy ray-curable resin.

The film of the present invention can be obtained by forming the thermoplastic resin composition of the present invention using any film forming apparatus. Examples of the film forming apparatus include a calendar roll rolling machine and a calendar roll rolling film forming apparatus comprising a take-up device; and a T-die film forming apparatus comprising an extruder, a T die, and a take-up device. etc. can be mentioned.

Examples of the calender roll mill include upright 3-rolls, upright 4-rolls, L-4 rolls, reverse L-4 rolls, and Z-rolls. Examples of the extruder include a single-screw extruder, a co-rotating twin-screw extruder, and a counter-rotating twin-screw extruder. Examples of the T-die include a manifold die, a fishtail die, and a coat hanger die.

The film of the present invention can be obtained by forming the thermoplastic resin composition of the present invention preferably using a calender roll rolling film forming apparatus. More preferably, it can be obtained by using a calender roll rolling film forming apparatus and forming a film at a roll temperature of 160°C to 200°C.

Although the thickness of the film of the present invention is not particularly limited, it 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 thinner articles containing the film of the present invention, the thickness is usually 1000 μm or less, preferably 500 μm or less, more preferably 200 μm or less.
In one aspect, the thickness of the film may be generally 20 μm to 1000 μm, preferably 20 μm to 500 μm, 20 μm to 200 μm, 50 μm to 1000 μm, 50 μm to 500 μm, or 50 μm to 200 μm.

The laminated film of the present invention is the film of the present invention (a film made of the thermoplastic resin composition of the present invention, typically a film made of the polyvinyl chloride resin composition of the present invention or an amorphous or low It is a laminated film containing one or more layers of a film made of a crystalline polyester-based resin composition. The laminated film of the present invention usually has, in order from the surface layer side, a coating film formed using a paint containing an active energy ray-curable resin and a layer of the film of the present invention.

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

The laminated film of the present invention has, for example, a coating film formed using a paint containing an active energy ray-curable resin, a layer of the film of the present invention, a printed layer, and a layer of a colored resin film, in this order from the surface layer side. Laminated films can be mentioned. Laminated films of such embodiments are used as decorative sheets and decorative films, home electric appliances such as refrigerators, washing machines, air conditioners, mobile phones, and personal computers; furniture such as decorative shelves, storage chests, cupboards, and desks; It can be suitably used for decorative makeup of building members such as walls and bathrooms. In such a laminated film, the film of the present invention is preferably transparent.

The total light transmittance of the film of the present invention (measured according to JIS K7105:2011 5.5.2 Measurement Method A) is usually 60% or more, preferably 70% or more, more preferably 80% or more, still more preferably 85 % or more, most preferably 90% or more. The higher the total light transmittance, the better. The total light transmittance can be measured according to JIS K7105:2011, 5.5.2 Measurement Method A, using, for example, a spectrophotometer "V-570" (trade name) manufactured by JASCO Corporation.

The printed layer in the laminated film is provided to impart a high degree of designability, and can be formed by printing any pattern using any ink and any printing machine.

The print layer can be applied entirely or partially on the front surface of the colored resin film directly or via an anchor coat. Patterns include metallic patterns such as hairlines, wood grain patterns, stone grain patterns that imitate the surface of rocks such as marble, fabric patterns that imitate texture or cloth patterns, tile patterns, brickwork patterns, marquetry patterns, and patchwork.
As the printing ink, a mixture of a binder, a pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like can be used. Examples of the binder include polyurethane resins, vinyl chloride/vinyl acetate copolymer resins, vinyl chloride/vinyl acetate/acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, and polyamides. resins such as cellulose-based resins, butyral-based resins, polystyrene-based resins, nitrocellulose-based resins, and cellulose acetate-based resins, and resin compositions thereof. In addition, in order to give a metallic design, aluminum, tin, titanium, indium and their oxides are applied directly or via an anchor coat to the front surface of the colored resin film, wholly or partially. Alternatively, it may be vapor-deposited by a known method.

The colored resin film in the laminated film is not particularly limited, but for example, polyester-based resins such as aromatic polyesters and aliphatic polyesters; acrylic-based resins; polycarbonate-based resins; poly(meth)acrylimide-based resins; polyethylene and polypropylene. , and polyolefin-based resins such as polymethylpentene; cellulose-based resins such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), styrene-ethylene- Styrene resins such as butadiene/styrene copolymers, styrene/ethylene/propylene/styrene copolymers, and styrene/ethylene/ethylene/propylene/styrene copolymers; polyvinyl chloride resins; polyvinylidene chloride resins; fluorine-containing resins such as vinylidene chloride; other examples include polyvinyl alcohol, ethylene vinyl alcohol, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, and polyethersulfone. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. Moreover, the colored resin film includes a laminated film sheet obtained by laminating two or more layers of one or more of these.

FIG. 2 is a schematic cross-sectional view showing an example of a decorative sheet using the film of the present invention. In order from the surface layer side, it has a coating film 1 formed using a paint containing an active energy ray-curable resin, a transparent film layer 2 of the present invention, a printed layer 3, and a colored thermoplastic resin film layer 4. are doing. A pressure-sensitive 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 laminated with the printed layer 3 .

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Measurement method (i) Total light transmittance JIS K7105: According to 5.5.2 measurement method A of 2011, using a spectrophotometer "V-570" (trade name) of JASCO Corporation, total light transmittance was measured.

(ii) Yellowing resistance In accordance with JIS Z8722: 2009, using a spectrophotometer "CM600d" (trade name) of Konica Minolta Japan Co., Ltd., geometric condition c, under conditions including specular reflection components, XYZ coordinates L*a*b* coordinates before treatment were obtained by measuring and converting this. Subsequently, irradiation with 50 KGy of γ-rays using cobalt-60 as a radiation source was performed. 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 for stabilizing the color of the sample, since the color yellowing of the sample gradually progresses for a while after irradiation. The L*a*b* coordinates after processing were determined according to the method described above. From the L*a*b* coordinates before processing and the L*a*b* coordinates after processing, the color difference (ΔE) is calculated using the calculation method (ΔE*ab (CIE1976)) built into the spectrophotometer. and evaluated the yellowing resistance. For the L*a*b* coordinates, the website of Konica Minolta Japan Co., Ltd. (address below) can be referred to.
http://www. konicaminolta. jp/instruments/knowledge/color/part1/07. html

(iii) Heat resistance After irradiation with 50 KGy of γ-rays using cobalt 60 as a radiation source, the sample after irradiation was allowed to stand under constant temperature and humidity conditions (temperature 23 ° C., relative humidity 50%) for 3 days. In accordance with Z8722:2009, using a spectrophotometer "CM600d" (trade name) of Konica Minolta Japan Co., Ltd., measure the XYZ coordinates under geometric conditions c and conditions including specular reflection components, and convert them. Thus, the L*a*b* coordinates before heat treatment were obtained. Subsequently, it was treated in a gear oven at a temperature of 70 ° C. (no humidity control) for 7 days, and further left to stand under constant temperature and humidity conditions (temperature of 23 ° C., relative humidity of 50%) for 3 days. L*a*b* coordinates after heat treatment were obtained according to the method of . From the L*a*b* coordinates before heat treatment and the L*a*b* coordinates after heat treatment, the color difference (ΔE) is calculated using the calculation method (ΔE*ab (CIE1976)) incorporated in the spectrophotometer. and evaluated the heat resistance.

(iv) Thermal Cycle Irradiation with 50 KGy of γ-rays using cobalt 60 as a radiation source was performed, and after irradiation, the sample was allowed to stand for 3 days under constant temperature and humidity conditions (temperature 23° C., relative humidity 50%). After that, according to JIS Z8722: 2009, using a spectrophotometer "CM600d" (trade name) of Konica Minolta Japan Co., Ltd., under conditions including geometric condition c and a component that becomes specular reflection, XYZ coordinates are measured. By converting , the L*a*b* coordinates before the thermal cycle treatment were obtained. Subsequently, thermal cycle treatment was performed with a program of 2 days at 50°C and 80% relative humidity, 1 day at 10°C (no humidity control), and 1 day at 50°C and 80% relative humidity. Furthermore, after standing still for 3 days under constant temperature and humidity conditions (temperature 23° C., 50% relative humidity), the L*a*b* coordinates after the cooling/heating cycle were obtained according to the method described above. From the L*a*b* coordinates before the cooling/heating cycle and the L*a*b* coordinates after the cooling/heating cycle, the color difference (ΔE) is calculated using the built-in calculation method (ΔE*ab (CIE1976)) of the spectrophotometer. was calculated, and this was used to evaluate the resistance to cold and heat changes.

(v) Weather resistance Irradiated with 50 KGy of γ-rays using cobalt 60 as a radiation source, and after irradiation, the sample was allowed to stand under constant temperature and humidity conditions (23°C, 50% relative humidity) for 3 days. After that, according to JIS Z8722: 2009, using a spectrophotometer "CM600d" (trade name) of Konica Minolta Japan Co., Ltd., under conditions including geometric condition c and a component that becomes specular reflection, XYZ coordinates are measured. were converted to obtain L*a*b* coordinates before treatment. Subsequently, using a sunshine carbon arc lamp type weather resistance tester (SWOM) “Sunshine Weather Meter S300” (trade name) of Suga Test Instruments Co., Ltd. specified in JIS B7753: 2007, the irradiance was measured at 225 W / m ² ( The specifications of the glass filter are type A in Table 2 of the above standard, the irradiance classification is normal type in Table 3 of the above standard), water spray for 18 minutes every 120 minutes, ambient temperature 43°C, black panel temperature 63°C , and treated for 2000 hours under conditions of 50 ± 5% relative humidity, and after standing for 3 days under constant temperature and humidity conditions (temperature 23 ° C., 50% relative humidity), L after treatment according to the method described above. *a*b* coordinates were determined. From the L*a*b* coordinates before processing and the L*a*b* coordinates after processing, the color difference (ΔE) is calculated using the calculation method (ΔE*ab (CIE1976)) built into the spectrophotometer. and evaluated the weather resistance.

(vi) Migration 1
Using a mixture of 100 parts by mass of ABS resin "Denka ABS GR-2000" (trade name) of Denka Co., Ltd. and 2 parts by mass of carbon black masterbatch (ABS resin base, 50% by mass of carbon), by injection molding, A square resin plate with a side of 15 cm and a thickness of 2 mm was obtained. Next, a sample (film cut into a rectangle of 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 (8 cm long, 6 cm wide, 2 mm thick) is placed on the surface of the sample. ) were superimposed so that the sample and the stainless steel plate substantially coincided when viewed from above. Subsequently, a weight of 1 kg was placed on the center of the surface of the stainless steel plate, and treatment was performed for 7 days in a gear oven at a temperature of 70° C. (no humidity control was performed). After the treatment, the contact points of the resin plate with the sample were visually observed and evaluated according to the following criteria. FIG. 3 is a photograph showing an example of D evaluation.
A: No change was observed at the contact point.
B: Slight discoloration was observed when the contact portion and the non-contact portion were compared. However, there was no part that lost its luster.
C: The contact portion was discolored, and a portion that lost glossiness was produced.
D: The contact area was remarkably discolored and lost its gloss over a wide area. It became frosty.

(vii) Migration 2
The migration was evaluated in the same manner as in (vi) above, except that polystyrene "Toyo Styrol HI H450" (trade name) from Toyo Styrene Co., Ltd. was used instead of the ABS resin.

Raw materials used (A) Amorphous or low-crystalline polyester resin (A-1) Eastman Chemical Company's amorphous aromatic polyester resin "KODAR PETG GS1" (trade name): (1) Terephthalic acid 100 mol% of structural units derived from, and (2) 66 mol% of structural units derived from ethylene glycol, 31 mol% of structural units derived from 1,4-cyclohexanedimethanol, and 3 mol% of structural units derived from diethylene glycol. Glycol-modified polyethylene terephthalate containing, glass transition temperature 81°C, heat of fusion 0 J/g (no clear melting peak in DSC second melting curve).
(A-2) Eastman Chemical Company's low-crystalline aromatic polyester resin "EASTER PCTG 5445" (trade name): (1) 100 mol% of structural units derived from terephthalic acid, and (2) derived from ethylene glycol Glycol-modified polyethylene terephthalate containing 35 mol% of structural units, 63 mol% of structural units derived from 1,4-cyclohexanedimethanol, and 2 mol% of structural units derived from diethylene glycol, glass transition temperature 85 ° C., DSC second melting curve Heat of fusion 11 J/g.

(B) Polyvinyl chloride resin (B-1) Polyvinyl chloride homopolymer having a degree of polymerization of 800.

(C) Core-shell rubber (C-1) Mitsubishi Chemical Corporation core-shell rubber (methyl methacrylate/styrene/ethyl acrylate rubber graft copolymer) “METABLEN W-300A” (trade name)

(D) Polyester plasticizer (D-1) Polyester plasticizer “ADEKA CIZER PN-280” (trade name) from ADEKA Corporation. Weight average molecular weight (Mw) 5200.
(D-2) ADEKA Corporation's polyester plasticizer "ADEKA CIZER PN-446" (trade name). Weight average molecular weight (Mw) 5300.
(D-3) DIC Corporation's polyester plasticizer "Polycizer W-4010" (trade name). Mass average molecular weight (Mw) 10,000.

(D'-1) ADEKA Corporation's polyester plasticizer "ADEKA CIZER PN-7160" (trade name). Weight average molecular weight (Mw) 1200.
(D'-2) Bis(2-ethylhexyl) phthalate.

(E) Optional components (E-1) Dioctyltin mercapto-based stabilizer "ADEKA STAB 465" (trade name) from ADEKA Corporation.
(E-2) ADEKA Corporation's lubricant "ADEKA STAB LS-16" (trade name).
(E-3) Mitsubishi Chemical Corporation's acrylic processing aid "P-530A" (trade name).

Examples 1-12
Using a co-rotating twin-screw extruder, the various components of the formulation (parts by weight) shown in Table 1 were melt-kneaded at a die outlet resin temperature of 160° C. to obtain a thermoplastic resin composition. Next, using a film forming apparatus equipped with an inverted L-shaped four calendar roll rolling machine and a take-up device manufactured by 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 180° C. for the fourth roll, and 60 m/min for take-up speed. The above tests (i) to (vii) were performed on this film. The results are shown in Table 1 or 2. The numbers in parentheses in the table are the compounding amounts (parts by mass) per 100 parts by mass of component (B).

From these results, it was found that the thermoplastic resin composition of the present invention is excellent in yellowing resistance and transparency. In addition, it was found that the preferable thermoplastic resin composition of the present invention suppresses troubles due to migration of the plasticizer. In addition, these thermoplastic resin compositions were also good in the heat resistance, thermal cycle, and weather resistance test results after γ-ray irradiation.

1: A coating film formed using a paint containing an active energy ray-curable resin 2: A layer of a transparent film of the present invention 3: A printed layer 4: A layer of a colored thermoplastic resin film

Claims (6)

A thermoplastic resin composition for a substrate of a coating film formed from a coating containing an active energy ray-curable resin,
(A) 1 to 100% by mass of amorphous or low-crystalline polyester resin; and (B) 99 to 0% by mass of polyvinyl chloride resin
100 parts by mass of a resin mixture in which the sum of the component (A) amorphous or low-crystalline polyester resin and the component (B) polyvinyl chloride resin is 100% by mass; and (C) A thermoplastic resin composition containing 1 to 100 parts by mass of core-shell rubber. A thermoplastic resin composition for a substrate of a coating film formed from a coating containing an active energy ray-curable resin,
(A) 1 to 99% by mass of amorphous or low-crystalline polyester resin; and (B) 99 to 1% by mass of polyvinyl chloride resin
100 parts by mass of a resin mixture in which the sum of the component (A) amorphous or low-crystalline polyester resin and the component (B) polyvinyl chloride resin is 100% by mass; and (C) including 1 to 100 parts by mass of core-shell rubber,
Furthermore, with respect to 100 parts by mass of the component (B) polyvinyl chloride resin,
(D) A resin composition containing 1 to 250 parts by mass of a polyester plasticizer. 3. The thermoplastic resin composition according to claim 2, wherein the component (D) polyester plasticizer has a mass average molecular weight of 3,100 or more. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 3. A film formed from the thermoplastic resin composition according to any one of claims 1 to 3. From the surface side,
A laminate film comprising: a coating film formed from a paint containing an active energy ray-curable resin; and a layer of the film according to claim 5 as a substrate.

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