JP7199193B2 - Polyvinyl chloride resin composition having insect repellent function, and anti-glass scattering film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyvinyl chloride resin composition having an insect repellent function, and a shatterproof glass film using the resin composition.

Conventionally, for the purpose of protecting and preventing scattering of glasses such as window glasses of buildings, windows of automobiles, and display faceplates of image display devices, resin films have been used by being attached to the glasses. In recent years, there has been growing interest in infectious diseases such as dengue fever carried by mosquitoes, and in highly toxic foreign insects such as fire ants. On the other hand, in recent years, from the viewpoint of environmental problems, insect repellents have low toxicity to organisms other than insects (toxicity to warm-blooded animals such as mammals and birds, toxicity to fish, etc.), and low persistence in the environment. is required. However, since such insect repellents are easily decomposed by ultraviolet rays, when they are used to impart insect repellent functions, they cannot be used in articles that are exposed to sunlight, such as anti-scattering glass films. There was a problem that the function was lost in a short time.

JP 2011-132375 A

An object of the present invention is to provide a polyvinyl chloride resin composition having an insect repellent function, and a shatterproof glass film using the resin composition. A further object of the present invention is to provide a polyvinyl chloride-based resin composition having an excellent long-lasting insect repellent function, and a shatterproof glass film using the resin composition.

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

That is, the present invention
(A) polyvinyl chloride resin 100 parts by mass;
(B) pyrethroid compound 0.01 to 100 parts by mass; and,
(C) UV absorber 0.01 to 20 parts by mass;
It is a polyvinyl chloride resin composition containing.

A second invention is the polyvinyl chloride resin composition according to the first invention, wherein the component (C) UV absorber contains (C2) a benzotriazole UV absorber.

A third invention is the polyvinyl chloride resin composition according to the first invention or the second invention, wherein the component (C) UV absorber contains (C1) a cyanoacrylate UV absorber.

A fourth invention is any one of the first to third inventions, wherein the component (C) ultraviolet absorber is a mixture of (C1) a cyanoacrylate-based ultraviolet absorber and (C2) a benzotriazole-based ultraviolet absorber. It is the described polyvinyl chloride resin composition.

A fifth invention is any one of the first to fourth inventions, further comprising 1 to 250 parts by mass of a polyester plasticizer (D) in addition to 100 parts by mass of the component (A) polyvinyl chloride resin It is the described polyvinyl chloride resin composition.

A sixth invention is the polyvinyl chloride resin composition according to the fifth invention, wherein the weight average molecular weight of the component (D) polyester plasticizer is 3100 or more.

A seventh invention is based on the first to sixth inventions, further comprising 0.1 to 10 parts by mass of a barium-zinc composite compound-based thermal stabilizer for 100 parts by mass of the component (A) polyvinyl chloride resin. 1. A polyvinyl chloride resin composition according to any one of the above.

An eighth invention is the composition according to any one of the first to seventh inventions, further comprising (E) 1 to 100 parts by mass of a core-shell rubber in addition to 100 parts by mass of the component (A) the polyvinyl chloride resin. It is a polyvinyl chloride resin composition.

A ninth invention is the polyvinyl chloride-based resin composition according to any one of the first to eighth inventions, which is used as a shatterproof film for glass.

A tenth invention is a glass shatterproof film comprising the polyvinyl chloride resin composition according to any one of the first to ninth inventions.

An eleventh invention is a molded article containing the polyvinyl chloride resin composition according to any one of the first to eighth inventions.

The polyvinyl chloride resin composition of the present invention has an insect repellent function. A preferable polyvinyl chloride-based resin composition of the present invention has an insect repellent function, and the deterioration of the insect repellent function when exposed to sunlight is suppressed. Therefore, it can be suitably used as a material for articles used in an environment exposed to sunlight, such as a glass scattering prevention film.

In this specification, the term "resin" is used as a term including 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." 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. 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.

In this specification, the term "greater than or equal to" regarding a numerical range is used to mean a certain numerical value or more 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.

As used herein, the term "insect repellent function" includes both the function of preventing insects from approaching (repellent function) and the function of killing insects (insecticidal function).

1. Polyvinyl chloride resin composition:
The polyvinyl chloride-based resin composition of the present invention contains (A) a polyvinyl chloride-based resin, (B) a pyrethroid-based compound, and (C) an ultraviolet absorber. In one preferred embodiment, the polyvinyl chloride resin composition of the present invention comprises (A) a polyvinyl chloride resin, (B) a pyrethroid compound, (C) an ultraviolet absorber, and (D) a polyester plasticizer. containing agents. Each component will be described below.

(A) Polyvinyl chloride resin:
The component (A) is a polyvinyl chloride resin. Examples of polyvinyl chloride resins 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, Vinyl chloride/methyl (meth)acrylate copolymer, vinyl chloride/ethyl (meth)acrylate copolymer, vinyl chloride/maleic acid ester copolymer, vinyl chloride/ethylene copolymer, vinyl chloride/propylene copolymer Copolymer, vinyl chloride/styrene copolymer, vinyl chloride/isobutylene copolymer, vinyl chloride/vinylidene chloride copolymer, vinyl chloride/styrene/maleic anhydride terpolymer, vinyl chloride/styrene/acrylonitrile terpolymer Polymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylonitrile copolymer , Vinyl chloride-based copolymers of vinyl chloride and other monomers copolymerizable with vinyl chloride, such as vinyl chloride and various vinyl ether copolymers; modified (chlorinated, etc.) polymers; and the like. 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. One or a mixture of two or more thereof can be used as the component (A).

(B) pyrethroid compound:
The component (B) is a pyrethroid compound. The above component (B) functions to develop an insect repellent function.

Examples of the component (B) include natural pyrethroids such as pyrethrin 1, pyrethrin 2, synerin 1, synerin 2, jasmolin 1, and jasmolin 2; Synthetic pyrethroid compounds such as cyphenothrin, veratrine, silafluofen, and etofenprox (2-(4-ethoxyphenyl)-2-methylpropyl=3-phenoxybenzyl ether, CAS registry number 80844-07-1); I can give Among these, from the viewpoint of low toxicity to organisms other than insects (toxicity to warm-blooded animals such as mammals and birds, toxicity to fish, etc.), low persistence in the environment, and insect repellent function Fenprox is preferred. One or a mixture of two or more thereof can be used as the component (B).

The amount of component (B) is usually 0.01 part by mass or more, preferably 0.1 part by mass, based on 100 parts by mass of component (A), from the viewpoint of insect repellent function and sustainability of insect repellent function. Above, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more. On the other hand, the upper limit of the amount of component (B) is appropriately determined from the viewpoint of moldability of the polyvinyl chloride resin composition. When the polyvinyl chloride resin composition of the present invention is applied to an injection molding method, it is usually 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less. It's okay. When the polyvinyl chloride-based resin composition of the present invention is applied to a calender rolling film-forming method, it may be generally 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less.

(C) UV absorber:
The above component (C) is an ultraviolet absorber. The above component (C) protects the above component (B) from being decomposed by ultraviolet rays, and functions to maintain the insect repellent function of the polyvinyl chloride resin composition of the present invention for a long period of time even in an environment exposed to sunlight. do. In addition, the component (C) functions to improve the weather resistance of the polyvinyl chloride resin composition of the present invention.

As the component (C), an organic compound ultraviolet absorber; zinc oxide, titanium oxide, calcium carbonate, cerium oxide, silica, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, carbon black, white carbon, zeolite, and Inorganic ultraviolet absorbers such as graphite; When the polyvinyl chloride-based resin composition of the present invention is used in applications requiring transparency such as a glass shatterproof film, from the viewpoint of transparency, an organic compound-based ultraviolet absorber is used as the component (C). preferable. As the component (C), from the viewpoint of the protective effect of the component (B) and the yellowing resistance of the polyvinyl chloride resin composition, the component (C1) cyanoacrylate ultraviolet absorber, or (C2) benzo Those containing a triazole-based ultraviolet absorber are more preferable. It is more preferable to contain (C1) a cyanoacrylate UV absorber and (C2) a benzotriazole UV absorber. A mixture of the component (C1) cyanoacrylate UV absorber and the component (C2) benzotriazole UV absorber is most preferred.

(C1) Cyanoacrylate UV absorber:
The component (C1) cyanoacrylate ultraviolet absorber is an organic compound having one or more cyanoacrylate skeletons in the molecule. Examples of the component (C1) include ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and pentaerythritol tetrakis(3,3-diphenyl-2 -cyanoacrylate). As the component (C1), one or a mixture of two or more thereof can be used.

(C2) Benzotriazole-based UV absorber:
The component (C2) benzotriazole-based ultraviolet absorber is an organic compound having one or more benzotriazole skeletons in the molecule. The above component (C2) may typically be a phenol compound having one or more benzotriazole skeletons in the molecule. Examples of the component (C2) include 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol, 2-(2H-benzotriazol-2-yl)- 4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2 '-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] and 2-(2H-benzotriazol-2-yl)-p - Cresol can be given. As the component (C2), one or a mixture of two or more thereof can be used.

(C3) Other organic compound-based UV absorbers:
An organic compound-based ultraviolet absorber other than the component (C1) cyanoacrylate-based ultraviolet absorber and the component (C2) benzotriazole-based ultraviolet absorber that can be used as the component (C) (hereinafter referred to as "component (C3) other (Sometimes abbreviated as "organic compound-based ultraviolet absorber".) Examples include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, aromatic benzoate-based ultraviolet absorbers, and oxalic acid anilide-based ultraviolet absorbers. can be done.

Examples of the triazine-based ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Examples of the benzophenone-based ultraviolet absorbers include [2-hydroxy-4-(octyloxy)phenyl](phenyl)methanone, 2,2′,4,4′-tetrahydroxybenzophenone, and 2,2′-dihydroxy -4,4'-dimethoxybenzophenone and the like can be mentioned.

Examples of the aromatic benzoate ultraviolet absorbers include 4-tert-butylphenyl salicylate, 4-octylphenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl- 4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, and the like.

Examples of the oxalic acid anilide-based UV absorber include 2-ethyl-2'-ethoxyoxanylide and 2-ethoxy-4'-dodecyloxanylide.

As the component (C3), one or a mixture of two or more thereof can be used.

The amount of the above component (C) is usually 0 per 100 parts by mass of the above component (A), from the viewpoint of weather resistance and from the viewpoint of sustaining the insect repellent function for a long time even in an environment exposed to sunlight. 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and most preferably 1.5 parts by mass or more. On the other hand, from the viewpoint of suppressing the trouble that the component (C) bleeds out on the film surface, it is usually 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 4 parts by mass or less. Most preferably, it may be 3 parts by mass or less.

When using a mixture of the component (C1) and the component (C2), from the viewpoint of obtaining a synergistic effect of both, the mixing ratio of the component (C1) and the component (C2) (the component (C1) (parts by mass)/(parts by mass) of component (C2)) is usually 20/1 to 1/20, preferably 10/1 to 1/10, more preferably 5/1 to 1 /5, more preferably 3/1 to 1/3, most preferably 2/1 to 1/2.

(D) polyester plasticizer:
If desired, the polyvinyl chloride resin composition of the present invention may further contain a plasticizer commonly used in polyvinyl chloride resin compositions. As the plasticizer, (D) a polyester-based plasticizer is preferable from the viewpoint of weather resistance.

Examples of the component (D) include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, and 1,4-butane. Diol, 1,5-hexanediol, 1,6-hexanediol, and neopentyl glycol, etc., using one or a mixture of two or more; using one or a mixture of two or more of glutaric acid, adipic acid, trimellitic acid, pimelic acid, suberic acid, maleic acid, azelaic acid, sebacic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid; If desired, monohydric alcohol, monocarboxylic acid or the like may be used as a stopper.

Polystyrene conversion obtained from a differential molecular weight distribution curve (hereinafter sometimes abbreviated as "GPC curve") measured by gel permeation chromatography (hereinafter sometimes abbreviated as "GPC") of the component (D) The mass average molecular weight (Mw) is usually 3,100 or more, preferably 3,500,000 or more, more preferably 4,000 or more, still more preferably 4,500 or more, and most preferably 4,500 or more, from the viewpoint of suppressing troubles due to migration of the plasticizer and from the viewpoint of yellowing resistance. Preferably, it may be 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.

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 feed pump, an autosampler, a column oven and an RI (differential refractive index) detector). ) as GPC columns; Shodex's GPC column "KF-806L (trade name)" two, "KF-802 (trade name)" and "KF-801 (trade name)" each one A total of four tubes are connected in order of KF-806L, KF-806L, KF-802, and KF-801 from the upstream side and used; ) as a 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 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 standard polystyrene "EasiCal PS-1 (trade name)" (Plain A molecular weight 6375000, 573000, 117000, 31500, 3480; Plain 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 actual measurement of GPC, refer to 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. You can refer to it.

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.

One or a mixture of two or more thereof can be used as the component (D).

The amount of component (D) is not particularly limited because it is an optional component. The amount of component (D) is usually 250 parts by mass based on 100 parts by mass of component (A) from the viewpoint of calendar roll rolling film formability, anti-blocking properties, and prevention of troubles due to migration of plasticizer. Below, 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, even 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 amount of component (D) is usually 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass, from the viewpoint of yellowing resistance, weather resistance, and calendar roll rolling film formability. parts or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more.

(E) Core shell rubber:
If desired, the polyvinyl chloride resin composition of the present invention may further contain a component (E) core-shell rubber commonly used in polyvinyl chloride resin compositions. The above component (E) functions to improve film formability by calender roll rolling.

Examples of the component (E) 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/acrylate rubber graft copolymer, methacrylate/acrylate rubber graft copolymer , a methacrylate/styrene/acrylate rubber graft copolymer, and a methacrylate/acrylonitrile/acrylate rubber graft copolymer. 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 and acrylics obtained by graft copolymerization of (meth)acrylic acid ester rubbers with (meth)acrylic acid esters, acrylonitrile, styrene, etc., such as methacrylic acid ester/acrylonitrile/acrylic acid ester rubber graft copolymers system core-shell rubbers are preferred. As used herein, "(meth)acrylic acid" means acrylic acid or methacrylic acid. One or a mixture of two or more thereof can be used as the component (E).

The amount of component (E) is not particularly limited because it is an optional component. The amount of the component (E) is usually 1 part by mass or more per 100 parts by mass of the component (A), from the viewpoint of reliably obtaining the effect of improving film-forming properties by calendar roll rolling and from the viewpoint of weather resistance. It may be 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, 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 even more preferably 20 parts by mass or less.

It is preferable that the polyvinyl chloride resin composition of the present invention further contains a heat stabilizer that is commonly used in polyvinyl chloride resin compositions. Examples of the heat stabilizer include barium-zinc composite compound-based, calcium-zinc composite compound-based, organic tin compound-based, and lead compound-based heat stabilizers. Among these, barium-zinc composite compound-based heat stabilizers are preferred from the viewpoint of sustainability of the insect repellent function. 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 (A), from the viewpoint of yellowing resistance. It may be more than part. On the other hand, from the viewpoint of suppressing bleeding out of the heat stabilizer, it may be usually 10 parts by mass or less, preferably 7 parts by mass or less, more preferably 5 parts by mass or less.

If desired, the polyvinyl chloride-based resin composition of the present invention may further contain components other than the components (A) to (E) as long as the objects of the present invention are not compromised. Examples of other components include thermoplastic resins other than components (A) and (E); insect repellents other than component (B); plasticizers other than component (D); light stabilizers and antioxidants. agents, weather stabilizers, colorants, lubricants, processing aids, nucleating agents, release agents, antistatic agents, urea-formaldehyde waxes, and additives such as surfactants;

Thermoplastic resins other than the components (A) and (E) 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; and an ethylene/ethyl (meth)acrylate copolymer can be mentioned.

Examples of insect repellents other than the component (B) include natural essential oils such as terpenes, sesquiterpenes, cinnamic acid amide derivatives, and flatoxins, and their derivatives; synthetic essential oils, phenylpyrazole compounds, organic phosphorus compounds, Examples include carbamate compounds and juvenile hormone-like compounds.

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 Examples include acid ester plasticizers and chlorine plasticizers.

It is preferable to use the component (D) polyester plasticizer and the epoxy plasticizer together. Effective against yellowing. Examples of the epoxy plasticizer include epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester. One or more of these can be used as the epoxy plasticizer.

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

The amount of the other components is not particularly limited because they are optional components, but 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.

The polyvinyl chloride-based resin composition of the present invention is prepared by using any melt-kneader to mix the above components (A) to (C) and any desired optional components at the same time or in any order with the melt-kneader. It can be obtained by pouring into and melt-kneading.

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; can give 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 body:
The molded article of the present invention is a molded article containing the polyvinyl chloride resin composition of the present invention. In the molded article of the present invention, the polyvinyl chloride resin composition of the present invention usually constitutes part or all of the surface of the molded article. The molded article of the present invention is usually a molded article intended to be used in an environment exposed to sunlight. Examples of such molded articles include films, sheets, and plates made of the polyvinyl chloride resin composition of the present invention; A composite molded article obtained by co-extrusion molding using a thermoplastic resin; a laminate of a film made of the polyvinyl chloride resin composition of the present invention and a film, sheet, or plate made of any thermoplastic resin; A composite molded body obtained by shaping the laminate by thermoforming such as vacuum molding, pressure molding, and press molding; and a film made of the polyvinyl chloride resin composition of the present invention as a skin material in a mold a composite molded article obtained by a method (film insert molding) in which an arbitrary thermoplastic resin is injected as a core material after inserting into the composite;

3. the film:
The film of the present invention is a film made of the polyvinyl chloride resin composition of the present invention. The film of the present invention can be obtained by forming a film using the polyvinyl chloride resin composition of the present invention using any film forming apparatus. Examples of the film forming apparatus include a calender 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. ; and so on.

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 using the polyvinyl chloride resin composition of the present invention and 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.

The thickness of the film of the present invention is not particularly limited, and can be any desired thickness. The thickness of the film of the present invention may be usually 10 µm or more, preferably 30 µm or more, and more preferably 50 µm or more, from the viewpoint of handleability and the viewpoint of conforming to the standards as a glass shatterproof film. On the other hand, from the viewpoint of meeting the demand for thinning the molded article containing the film of the present invention, it may be usually 1000 μm or less, preferably 500 μm or less, more preferably 250 μm or less, even more preferably 150 μm or less, and most preferably 100 μm or less. .

When using the film of the present invention for applications that require transparency such as a glass shatterproof film, the total light transmittance of the film of the present invention (measured according to 5.5.2 Measurement Method A of JIS K7105: 2011 ) may be usually 60% or more, preferably 70% or more, more preferably 80% or more, even more preferably 85% or more, and most preferably 88% 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.

4. Glass shatterproof film:
The glass shatterproof film of the present invention includes the film of the present invention. The shatterproof glass film of the present invention usually contains the film of the present invention as a component of at least one layer, and the layer of the film of the present invention forms the surface in actual use. The shatterproof film for glass of the present invention may be used by being attached to the indoor side such as window glass of a building, or may be used by being attached to the outdoor side.

As the glass shatterproof film of the present invention, for example, one having an adhesive layer and a layer of the film of the present invention in order from the bonding surface side with the glass; those having a layer; those having an adhesive layer, a functional layer, an anchor coat, and a layer of the film of the present invention;

The pressure-sensitive adhesive layer functions to bond the anti-scattering film for glass of the present invention to glass. The pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer is not particularly limited as long as it has sufficient adhesive strength to glass, and any pressure-sensitive adhesive can be used. As the pressure-sensitive adhesive, a transparent pressure-sensitive adhesive that has sufficient adhesive strength to glass and is transparent is preferable. Examples of the transparent adhesive include acrylic adhesives, urethane adhesives, and silicone adhesives. One or a mixture of two or more of these can be used as the transparent pressure-sensitive adhesive.

The adhesive may preferably contain an ultraviolet absorber. Weather resistance of adhesive strength can be enhanced. The amount of the ultraviolet absorber to be blended is preferably about 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably about 10 to 25 parts by mass with respect to 100 parts by mass of the base resin of the adhesive. good.

The pressure-sensitive adhesive may further contain optional components other than the pressure-sensitive adhesive component, as desired, as long as the object of the present invention is not compromised. Examples of the optional components include a photopolymerization initiator, a compound having two or more isocyanate groups in one molecule, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, an antifouling agent, and a printability improver. Additives such as agents, antioxidants, weather stabilizers, light stabilizers, heat stabilizers, pigments, inorganic particles, and organic particles can be mentioned. The amount of the above optional components to be blended is usually about 10 parts by mass or less, or about 0.01 to 10 parts by mass, per 100 parts by mass of the pressure-sensitive adhesive component.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but from the viewpoint of adhesive strength, it may be usually 5 µm or more, preferably 10 µm or more, more preferably 15 µm or more, and still more preferably 20 µm or more. On the other hand, from the viewpoint of thinning, the thickness is usually 100 μm or less, preferably 60 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less.

A method for forming the pressure-sensitive adhesive layer is not particularly limited, and may be any method. Examples of the above method include roll coating, gravure coating, reverse coating, die coating, dip coating, spray coating, spin coating, and air knife coating. A method of forming the pressure-sensitive adhesive layer directly or through an anchor coat can be mentioned. Examples of the above methods include roll coating, gravure coating, reverse coating, and die coating on the surface of any film substrate (e.g., biaxially stretched polyethylene terephthalate resin film, biaxially stretched polypropylene resin film, etc.). , dip coating, spray coating, spin coating, and air knife coating to form an adhesive layer, which is applied directly or via an anchor coat on the adhesive layer-formed surface of the film for attaching to the outside of the glass. , a method of transferring.

The anchor coating agent for forming the anchor coat is not particularly limited, and any anchor coating agent can be used. Examples of the anchor coating agent include polyester-based, acrylic-based, polyurethane-based, acrylic-urethane-based, and polyester-urethane-based anchor coating agents. One or a mixture of two or more of these can be used as the anchor coating agent.

The anchor coating agent may contain an ultraviolet absorber. The weather resistance of the adhesive strength between the functional layer and the layer of the film of the present invention can be enhanced. The amount of the ultraviolet absorber to be blended is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 25 parts by mass, and still more preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the base resin of the anchor coating agent. It may be about 15 parts by mass.

Antioxidants, weather stabilizers, light stabilizers, heat stabilizers, antistatic agents, surfactants, and infrared shielding agents may be added to the above anchor coating agents as desired, as long as they do not contradict the purpose of the present invention. One or more additives such as agents, leveling agents, thixotropic agents, antifouling agents, printability improvers, colorants, inorganic particles, and organic particles may be included.

In order to dilute the anchor coating agent to a concentration that facilitates coating, a solvent may be included as desired. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As the solvent, one or a mixture of two or more thereof can be used.

The anchor coating agent can be obtained by mixing and stirring these components.

A method for forming the anchor coat using the anchor coating agent is not particularly limited, and a known web coating method can be used. Examples of the method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

The thickness of the anchor coat is not particularly limited, but may be usually 0.01 μm or more, preferably 0.1 μm or more, from the viewpoint of adhesive strength between the functional layer and the film layer of the present invention. On the other hand, it may be usually 5 μm or less, preferably 2 μm or less.

Examples of the functional layer include those having functions such as infrared shielding, infrared reflection, electromagnetic wave shielding, electromagnetic wave reflection, visibility control (blindfold), and viewing angle control.

The functional layer is not limited to one layer, and may be two or more layers. When the number of functional layers is two or more, the number of the functional layers is not limited to one but may be two or more.

The thickness of the functional layer is appropriately selected in consideration of the function to be imparted, the method of forming the layer, and the like.

FIG. 2 is a cross-sectional conceptual diagram showing an example of a glass-scattering prevention film using the film of the present invention. The shatterproof glass film is used by being attached to the indoor side of the window glass of a building. It has a layer 4 of the film of the present invention.

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

Measurement method (a) Insect repellent function 1:
A test piece measuring 28 cm in the machine direction and 14 cm in the transverse direction was taken from the anti-glass shattering film and used as test film 5 . Next, a test film 5 is attached to one of the sidewalls of an acrylic resin test box (the inner dimensions of the box are 30 cm in width, 30 cm in depth, and 15 cm in height), and a control film 6, which will be described later, is attached to the opposite side wall, A petri dish 7 with a diameter of 6 cm containing 20 mL of a 5% by weight sucrose aqueous solution was placed in the center of the bottom of the box, and the upper opening of the test box was covered with a nylon gauze 8 (Fig. 3). Subsequently, 200 female Culex pipiens, 2 to 5 days old after emergence, were released inside the test box. After feeding, the number of Culex pipiens colonized on test film 5 and control film 6 was recorded every 4 hours. A total of 8 recordings were made (last recording 32 hours after feeding). The repelling rate (%) was calculated from the following formula (1). Here, α is the total number of Culex pipiens fixed on the test film 5, and β is the total number of Culex pipiens fixed on the control film 6.
(1-(α/β))×100 (1)

(A-2) Preparation of control film:
The following component (A-1) 100 parts by mass, the following component (C1-1) 1 part by mass, the following component (C2-1) 1 part by mass, the following component (D-1) 30 parts by mass, the following component (F-1) ) 2 parts by mass, 2 parts by mass of the following component (F-2), and 0.5 parts by mass of the following component (F-4), using a mixer kneader, the resin temperature at the time of discharge is 140 ° C. to obtain a polyvinyl chloride 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. Subsequently, on one side of the obtained film, using a roll coater, the following paint for forming an adhesive layer (S-1) was applied to a dry thickness of 15 μm, and dried in a drying oven to adhere. An agent layer was formed to obtain a glass scattering prevention film. A test piece measuring 28 cm in the machine direction and 14 cm in the transverse direction was taken from the resulting glass shatterproof film and used as Control Film 6 .

(b) Insect repellent function sustainability 1:
After treating the glass scattering prevention film under the following (B-2) treatment condition 1, the same test (B) insect repellent function 1 was performed except that it was accumulated in a size of 28 cm × 14 cm and used. . Further, the residual rate of the above component (B) was measured by the method of (b-4) below.

(B-2) Treatment condition 1:
Using an accelerated weather resistance tester "Metal Weather KW-R7TP (trade name)" manufactured by Daipla Wintes Co., Ltd., a glass shatterproof film is placed on the surface of a float plate glass (thickness 3mm). The adhesive layer side surface is on the glass side, and the obtained bonded body is set in the tester so that the glass scattering prevention film side surface of the bonded body is on the lamp light source side, The following (b-3) DMW test cycle was performed continuously for four cycles.

(b-3) DMW test cycle:
Water-cooled metal halide lamp, transmission wavelength range of 295 to 780 nm (using a KF-1 filter, adjusted to the wavelength distribution of sunlight), irradiation intensity of 70 mW/cm ² , black panel temperature of 53°C, and relative humidity of 50%. After performing irradiation treatment for 20 hours under the conditions, immediately spray pure water on the irradiated surface of the glass scattering prevention film for 10 seconds, without lamp irradiation, black panel temperature 30 ° C., relative humidity 98%. Immediately after the film was left in the dark for a period of time, pure water was sprayed for 10 seconds onto the irradiated surface of the anti-glass film. The above is one cycle of the DMW test cycle.

(B-4) Method for measuring residual rate of component (B):
(B-4-1) Sample preparation:
A shatterproof glass film (size: 50 mm x 10 mm) was dissolved in 2 mL of tetrahydrofuran (reagent special grade). Next, 18 mL of acetonitrile (reagent special grade) was added and well stirred to precipitate the resin component. Subsequently, the precipitate was filtered off using a polytetrafluoroethylene filter membrane (pore size: 0.45 μm) to obtain a sample.

(B-4-2) Measurement of the amount of the component (B) in the sample:
Using a gas chromatograph equipped with a mass spectrometer, one column of Agilent's dimethylpolysiloxane column "DB-1MS UI (trade name)" (length 20 m, inner diameter 0.18 mm, film thickness 0.18 μm) A solution of dibutylhydroxytoluene (reagent special grade) in tetrahydrofuran (reagent special grade) was added as an internal standard substance to the sample prepared in (B-4-1) above so that the concentration of dibutylhydroxytoluene in the sample was 0.005% by mass. A helium mobile phase, a split ratio of 30:1, a column flow rate of 1.35 mL/min, a measurement sample injection volume of 1 μL, and a column heating program of 100° C. and holding for 0.6 minutes, Chromatography measured under the conditions of a temperature increase rate of 35 ° C./min from 100 ° C. to 230 ° C., a temperature increase rate of 17.5 ° C./min from 230 ° C. to 300 ° C., and a hold at 300 ° C. for 6.0 minutes. From the graph, the peak area of the component (B) was obtained as an indicator of the amount of the component (B). At this time, from the peak area value of dibutylhydroxytoluene used as an internal standard substance, the peak area value of the component (B) was corrected between measurements according to a conventional method. Identification of the peak of the component (B), except that the 0.1 mass% acetonitrile (reagent special grade) solution of the component (B) was used as a sample, was measured in the same manner as the retention time of the peak appearing in the chromatograph went from Reference books such as "Capillary Gas Chromatography" published by Asakura Shoten Co., Ltd. and edited by the Japan Society for Analytical Chemistry Gas Chromatography Research Council can be referred to for the theory and actual measurement of gas chromatography.

(B-4-3) Calculation of residual ratio of component (B):
The residual rate (unit %) of the component (B) was calculated from the following formula.
B=B ₁ /B ₀ ×100
Here, B is the residual rate (unit %) of the component (B), and B ₀ is the component (B ), and B ₁ is an index of the amount of component (B) above in the sample prepared with the glass shatterproof film after the accelerated weathering test.

(C) Insect repellent function sustainability 2:
The processing conditions for the anti-scattering glass film were carried out in the same manner as in Test (b) Insect Repellent Function Sustainability 1 above, except that the number of DMW test cycles was changed from 4 to 8 cycles.

(c) Visible light transmittance:
Based on JIS A5759:2016 6.4 Visible light transmittance test, the surface of the glass scattering prevention film on the adhesive layer side was used as the bonding surface with the plate glass, and the film surface of the test piece was measured under the condition of facing the light source.

(d) Yellowness index:
Measured according to JIS K7105:1981 using a chromaticity meter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation.

(E) Yellowing resistance 1 (yellowness index after accelerated weather resistance test):
After treating the glass scattering prevention film in the same manner as the treatment condition 1 of the above test (b) Insect repellent function sustainability 1, according to JIS K7105: 1981, a color meter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation. was measured using

(F) Yellowing resistance 2 (yellowness index after accelerated weathering test):
Except that the number of DMW test cycles was changed from 4 to 8, the processing conditions for the anti-glass shattering film were treated in the same manner as in the processing conditions 1 of the above test (B) Insect repellent function sustainability 1. Measured according to JIS K7105:1981 using a chromaticity meter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation.

Raw materials used (A) polyvinyl chloride resin:
(A-1) Polyvinyl chloride homopolymer having a degree of polymerization of 1050.

(B) pyrethroid compound:
(B-1) Mitsui Chemicals Agro Co., Ltd.'s pyrethroid compound "etofenprox (trade name)". 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether.

(C) UV absorber:
(C1) Cyanoacrylate UV absorber:
(C1-1) Cyanoacrylate UV absorber “Ubinal 3039 (trade name)” from BASF. 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate.
(C1-2) Cyanoacrylate UV absorber “Ubinal 3035 (trade name)” from BASF. Ethyl-2-cyano-3,3-diphenyl acrylate.

(C2) Benzotriazole-based UV absorber:
(C2-1) BASF's benzotriazole-based UV absorber "TINUVIN 326 (trade name)". 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol.
(C2-2) ADEKA Corporation benzotriazole-based UV absorber "ADEKA STAB LA-32 (trade name)". 2-(2H-benzotriazol-2-yl)-p-cresol.

(C3) Other organic compound-based UV absorbers:
(C3-1) Benzophenone UV absorber "SEESORB106 (trade name)" from Shipro Kasei Co., Ltd.; 2,2',4,4'-tetrahydroxybenzophenone.

(D) Plasticizer:
(D-1) ADEKA Corporation's polyester plasticizer "ADEKA CIZER PN-280 (trade name)". 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-4) ADEKA Corporation's polyester plasticizer "ADEKA CIZER PN-7160 (trade name)". Weight average molecular weight (Mw) 1200.
(D-5) Bis(2-ethylhexyl) phthalate.
(D-6) "Sansocizer E-PO" by New Japan Chemical Co., Ltd. Bis(9,10-epoxystearyl) epoxyhexahydrophthalate.

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

(F) Optional ingredients:
(F-1) Mitsubishi Chemical Corporation's acrylic processing aid "P-530A (trade name)".
(F-2) Barium-zinc complex salt-based heat stabilizer “LT703N (trade name)” from Akishima Chemical Industry Co., Ltd.
(F-3) Dioctyltin mercapto-based heat stabilizer “ADEKA STAB 465 (trade name)” from ADEKA Corporation.
(F-4) Lubricant “ADEKA STAB LS-16 (trade name)” manufactured by ADEKA Corporation.

(S) Paint for forming an adhesive layer:
(S-1) Toyochem Co., Ltd. acrylic adhesive "Oribain BPS5296 (trade name)" 100 parts by mass, Toyochem Co., Ltd. isocyanate curing agent "Oribain BXX4773 (trade name)" 0.5 parts by mass (solid content conversion 0.2 parts by mass), 20 parts by mass of a benzophenone-based ultraviolet absorber (2,2',4,4'-tetrahydroxybenzophenone) "SEESORB106 (trade name)" from Shipro Kasei Co., Ltd., and 70 parts by mass of ethyl acetate. Paint obtained by mixing and stirring.

Examples 1-19
A resin composition having a formulation (parts by mass) shown in Table 1 was melt-kneaded using a mixer kneader at a discharge resin temperature of 140° C. to obtain a polyvinyl chloride 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. Subsequently, on one side of the obtained film, using a roll coater, the adhesive layer forming coating material (S-1) was applied to a dry thickness of 15 μm, and dried in a drying oven to adhere. An agent layer was formed to obtain a glass scattering prevention film. The above tests (a) to (f) were performed. The results are shown in any of Tables 1-3. "<10" in the table means that the repellency rate is less than 10%. "Residual rate" means the residual rate of component (B) after accelerated weathering treatment. "ND" means that the residual rate of component (B) after accelerated weathering treatment is less than 1%.

The glass shatterproof film using the polyvinyl chloride resin composition of the present invention exhibited a good insect repellent function. The anti-glass film using the preferred polyvinyl chloride resin composition of the present invention exhibited a good insect repellent function. In addition, since the insect repellent function after the accelerated weather resistance treatment was also good, it was found that the insect repellent function was excellent in sustainability. Furthermore, transparency, color tone, and yellowing resistance were also good.

4 is a differential molecular weight distribution curve of the component (D-1) used in Examples. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional conceptual diagram which shows an example of the glass-scattering prevention film of this invention. It is a conceptual diagram explaining an insect repellent function test.

1: Adhesive layer 2: Coating film having infrared shielding function 3: Anchor coat 4: Layer of the film of the present invention 5: Test film 6: Control film 7: Petri dish 8: Nylon gauze

Claims (11)

(A) polyvinyl chloride resin 100 parts by mass;
(B) pyrethroid compound 0.01 to 100 parts by mass; and,
(C) UV absorber 0.01 to 20 parts by mass;
wherein the component (C) UV absorber comprises (C1) a cyanoacrylate UV absorber,
Polyvinyl chloride resin composition.
2. The polyvinyl chloride resin composition according to claim 1, wherein the component (C) UV absorber contains (C2) a benzotriazole UV absorber.
3. The polyvinyl chloride resin composition according to claim 1, wherein the component (C) UV absorber is a mixture of (C1) a cyanoacrylate UV absorber and (C2) a benzotriazole UV absorber.
Mixing ratio of the component (C1) cyanoacrylate-based UV absorber and the component (C2) benzotriazole-based UV absorber (mixing amount (parts by mass) of component (C1)/mixing amount of component (C2) ( The polyvinyl chloride resin composition according to claim 3, wherein parts by mass)) is from 20/1 to 1/20.
The polyvinyl chloride system according to any one of claims 1 to 4, further comprising 1 to 250 parts by mass of a polyester plasticizer (D) with respect to 100 parts by mass of the component (A) polyvinyl chloride resin. Resin composition.
6. The polyvinyl chloride resin composition according to claim 5, wherein the component (D) polyester plasticizer has a mass average molecular weight of 3,100 or more.
7. The method according to any one of claims 1 to 6, further comprising 0.1 to 10 parts by mass of a barium-zinc composite compound-based thermal stabilizer with respect to 100 parts by mass of the component (A) polyvinyl chloride resin. Polyvinyl chloride resin composition.
The polyvinyl chloride resin composition according to any one of claims 1 to 7, further comprising 1 to 100 parts by mass of (E) a core-shell rubber with respect to 100 parts by mass of the component (A) polyvinyl chloride resin. thing.
The polyvinyl chloride-based resin composition according to any one of claims 1 to 8, which is used for a glass scattering prevention film.
A shatterproof glass film comprising the polyvinyl chloride resin composition according to any one of claims 1 to 9.
A molded article comprising the polyvinyl chloride resin composition according to any one of claims 1 to 8.

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