JPH1017743A - Method for producing vinyl chloride resin composition - Google Patents

Abstract

(57) [Problem] To provide a method for producing a vinyl chloride resin composition having excellent light storage properties and afterglow properties, and having good heat discoloration resistance, processing discoloration resistance and molding processability. A vinyl chloride resin contains at least one kind of a phosphorescent phosphor composed of a metal compound represented by the following general formula (1) and an activator and a metal element selected from zinc, tin, and lead. In a method for producing a vinyl chloride resin composition containing a stabilizer, a vinyl chloride resin and the stabilizer are preliminarily mixed to form a uniform mixture, and then the mixture and the phosphorescent phosphor are mixed or mixed. A method for producing a vinyl chloride resin composition, comprising kneading. General formula (1); MAl ₂ O ₄ (wherein, M represents at least one metal element selected from magnesium, calcium, strontium, and barium)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel vinyl chloride resin composition using a phosphorescent phosphor having excellent luminous and afterglow properties, and excellent in heat discoloration resistance, processing discoloration resistance and moldability. The present invention relates to a method for manufacturing a product.

[0002]

2. Description of the Related Art Conventionally, resin compositions having fluorescent properties include:
A zinc sulfide-based fluorescent agent is used. This composition has a drawback that the light storage time is short, the afterglow is poor, the use time is restricted, and it is difficult to use at night.

[0003]

A luminous phosphor having a long luminous time is disclosed in JP-A-7-11250.
JP-A-7-24 describes a vinyl chloride resin composition containing the phosphor.
No. 7391. This vinyl chloride resin composition is mainly composed of plastisol, and Example 7 describes an example of a vinyl chloride compound. The production of vinyl chloride compounds is usually
Together with vinyl chloride resin, plasticizer, phosphor, stabilizer, etc.
After stirring with a high-speed mixer represented by Henschel mixer,
It is manufactured by kneading. The present inventor mixed the above-mentioned phosphorescent phosphor with a vinyl chloride resin using a Henschel mixer and then kneaded the mixture. However, the vinyl chloride resin composition containing the phosphor is poor in heat resistance and easily blackened. As a result, a vinyl chloride resin composition having a long luminous time was not obtained.

The present inventor speculated that the cause of the blackening was caused by the collision between the luminous phosphor and the wall metal while the luminous phosphor was mixed by a high-speed mixer such as a Henschel mixer. Then, based on the presumption, the inventors studied intensively to produce a vinyl chloride resin composition having no thermal discoloration and processing discoloration and having a long luminous time, and mixed the luminous phosphor with the vinyl chloride resin in a low-speed mixer. Or, even when using a high-speed mixer, by selecting the time of addition of the phosphorescent phosphor to the vinyl chloride resin, and by using a heat stabilizer containing a specific metal element, without impairing the phosphorescence,
The present inventors have found that a vinyl chloride resin composition having excellent heat discoloration resistance and discoloration resistance during processing and good moldability can be obtained, thereby completing the present invention. That is, an object of the present invention is to provide a method for producing a vinyl chloride resin composition having excellent light storage properties and afterglow properties, and having good heat discoloration resistance, processing discoloration resistance, and molding processability.

[0005]

Means for Solving the Problems The gist of the present invention is that a phosphorescent phosphor comprising a metal compound represented by the following general formula (1) and an activator is added to a vinyl chloride resin. In a method for producing a vinyl chloride resin composition containing a stabilizer containing at least one metal element selected from zinc, tin or lead, a method in which a vinyl chloride resin is mixed in advance with the stabilizer to form a uniform mixture A method for producing a vinyl chloride resin composition, comprising mixing or kneading the mixture and the phosphorescent phosphor,
Alternatively, a luminous phosphor composed of a metal compound represented by the following general formula (1) and an activator and a stabilizer containing at least one metal element selected from zinc, tin or lead in a vinyl chloride resin. In the method for producing a vinyl chloride resin composition containing the compound, the components are mixed together in a low-speed mixer, and then kneaded, and the mixture is kneaded. General formula (1); MAl ₂ O ₄ (wherein, M represents at least one metal element selected from magnesium, calcium, strontium, and barium)

[0006]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail. The vinyl chloride-based resin used in the method for producing the vinyl chloride-based resin composition of the present invention is obtained by suspending vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable thereto with a suspension polymerization method, a bulk polymerization method, or a fine suspension. All those produced by ordinary methods such as a polymerization method or an emulsion polymerization method are used. Examples of the comonomer include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate; acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylates such as methyl methacrylate and ethyl methacrylate; and dibutyl. Maleates such as maleate and diethyl maleate; fumaric esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; cyanides such as acrylonitrile and methacrylonitrile Α of vinyl chloride, ethylene, propylene, styrene, etc.
-Olefins, vinylidene chloride, vinylidene halides other than vinyl chloride such as vinyl bromide or vinyl halides, diallyl phthalate, polyfunctional monomers such as ethylene glycol dimethacrylate, etc. However, the present invention is not limited to this. The comonomer is contained in the component of the vinyl chloride resin in an amount of 30% by weight or less, preferably 20% by weight or less.

The weight average polymerization degree of the vinyl chloride resin based on JIS K6721 is in the range of 500 to 10,000, preferably in the range of 600 to 4500. If the average degree of polymerization is less than 500, the weather resistance tends to be inferior, and if it exceeds 10,000, kneading and molding become difficult.

The category of the vinyl chloride resin also includes a chlorinated vinyl chloride resin obtained by post-chlorinating the vinyl chloride resin produced as described above. A polymer compound compatible with the vinyl chloride resin can be added to these vinyl chloride resins. Examples of such a polymer compound include an ethylene-vinyl acetate copolymer, an ethylene-acrylate copolymer, an ethylene-vinyl acetate-carbon monoxide copolymer, and a chlorinated polyethylene. It is added in a range of 150 parts by weight or less, preferably 100 parts by weight or less per 100 parts by weight of the system resin.

The phosphorescent phosphor used in the method of the present invention comprises:
The metal compound represented by the following general formula (1) activated by the activator is used as the fluorescent matrix. MAl ₂ O ₄ M in the general formula (1) is composed of at least one metal element selected from magnesium, calcium, strontium and barium, that is, magnesium aluminate, calcium aluminate , Strontium aluminate, barium aluminate, magnesium calcium aluminate, strontium calcium aluminate,
Examples include compounds of various structural formulas such as strontium barium aluminate, strontium magnesium aluminate, and barium magnesium aluminate. For example, the structural formula of strontium magnesium aluminate is represented by Sr _x Mg _1-x Al ₂ O ₄ .

The activator for activating the fluorescent matrix is at least one selected from rare earth elements, manganese, tin or bismuth, and may be activated by two or more. Examples of rare earth elements include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, promethium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and the like, and europium as an activator. Is preferably used as the coactivator.

The amount of the activator to be added is selected from the range of 0.001 to 10 mol% based on the metal element M in the general formula (1). The strontium magnesium aluminate activated by europium and dysprosium is indicated, for example, as follows. Sr _x Mg ₁ -x Al ₂ O ₄ : Eu, Dy The phosphorescent phosphor is usually supplied with a particle diameter of 100 mesh, and is 5 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin. It is used appropriately within the range of parts by weight.
The vinyl chloride resin composition of the high-concentration phosphor is diluted with another resin and used as a master batch. Normal use concentrations are in the range of 70 parts by weight or less per 100 parts by weight of the resin. When the content of the phosphorescent phosphor is less than 5 parts by weight, the afterglow is not sufficient, and when the content is 200 parts by weight or more, molding becomes difficult as it is.

[0012] The stabilizer contained in the vinyl chloride resin composition produced by the method of the present invention must contain at least one metal element selected from zinc, tin and lead. As long as the metal element is contained, another element may be combined or another stabilizer may be used in combination. If it does not contain these metal elements, it causes thermal discoloration to brown during kneading or molding during the production of the composition, that is, poor thermal stability, resulting in poor sharpness and poor afterglow. Come.

Examples of the stabilizer include metal soaps such as zinc stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexoate, tin stearate, lead stearate, dibasic lead stearate and lead naphthenate. Lead such as lead white, basic lead silicate, tribasic lead sulphate, tribasic lead phosphite, tribasic lead maleate, dibasic lead phthalate, silica gel coprecipitated lead silicate, normal salicylic san lead Salt stabilizers: dibutyltin dilaurate, dibutyltin malate,
Organotin stabilizers such as dibutyltin mercaptide; Ba-Z
n-based, Ca-Zn-based, Cd-Ba-Zn-based, Cd-Ba
—Pb-based, Ca—Mg—Zn-based composite stabilizers, and various stabilizers such as composite-type metal soaps.

The amount of the stabilizer to be added is 10
A suitable range is 0.05 to 20 parts by weight, preferably 0.1 to 6 parts by weight, based on 0 parts by weight. The amount of this addition
This is the amount during normal use of the composition. In the case of master batch production, it is desirable to add a large amount in consideration of the case of normal use. If the amount is less than 0.05 part by weight, the effect of thermal stability cannot be obtained, and various physical properties such as weather resistance of the vinyl chloride resin composition cannot be maintained. Further, even if it is added in an amount of more than 20 parts by weight, the effect of stability in proportion to the added amount cannot be expected, and it is desirable to appropriately determine from the above range in consideration of cost and the like.

The vinyl chloride resin composition produced by the method of the present invention can be used in combination with a plasticizer to soften the composition and facilitate kneading and processing.
The plasticizer is not particularly limited as long as it is generally used for a vinyl chloride resin. For example, dibutyl phthalate (DBP), dihexyl phthalate, di-2-yl
Phthalate plasticizers such as ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, or phthalate of higher alcohols having about 11 to 13 carbon atoms;

Di-2-ethylhexyl adipate, di-
n-octyl adipate, di-n-decyl adipate,
Aliphatic dibasic ester plasticizers such as diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate; tri-2-ethylhexyl trimellitate, tri-n-octyl trimellitate Trimellitate plasticizers such as tate, tridecyl trimellitate, triisodecyl trimellitate, di-n-octyl-n-decyl trimellilate;

Tributyl phosphate, tricresyl phosphate (TCP), triphenyl phosphate, trixylyl phosphate, trioctyl phosphate,
Octyl diphenyl phosphate, cresyl diphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (Bromochloropropyl) phosphate, bis (2,3-dibromopropyl) -2,
Phosphate plasticizers such as 3-dichloropropyl phosphate and bis (chloropropyl) monooctyl phosphate;

Biphenyltetracarboxylic acid tetraalkylester plasticizers such as 2,3,3 ', 4'-biphenyltetracarboxylic acid tetraheptyl ester; Polyester polymer plasticizers; Epoxidized soybean oil; Epoxidized linseed oil And epoxy plasticizers such as liquid epoxy resins; chlorinated paraffins; chlorinated fatty acid esters such as alkyl pentachloride stearate; and the like, and one or more of these may be used in combination. Then
The amount of the plasticizer to be added varies depending on the type of the vinyl chloride resin, the presence or absence or the amount of other additives such as a filler described below, but up to 200 parts by weight per 100 parts by weight of the vinyl chloride resin, preferably A range up to 150 parts by weight is suitable.

It is preferable to add an acrylic resin to the vinyl chloride resin composition produced by the method of the present invention. The addition promotes the meltability of the composition, improves the kneading properties and moldability, and improves the heat stability. Improve the performance. The acrylic resin is not particularly limited, but methyl methacrylate is 20 to 90% by weight, preferably 25 to 80% by weight.
And the remainder is a copolymer comprising 80 to 10% by weight, preferably 75 to 20% by weight, of at least one monomer selected from acrylates, methacrylates other than methyl methacrylate, and styrene. Is preferred. As the acrylate, for example, methyl acrylate, ethyl acrylate, butyl acrylate,
2-ethylhexyl acrylate and the like, and methacrylates include ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and the like. Such acrylic resins are available from Mitsubishi Rayon Co., Ltd. in the form of Metablen P-551 and Metablen P-70.
0 etc. are commercially available.

The proportion of the acrylic resin is 30 parts by weight or less based on 100 parts by weight of the vinyl chloride resin.
It is preferably in the range of 0.5 to 20 parts by weight, especially 1 to 12 parts by weight. If the compounding ratio is too small, the meltability of the resin composition is not sufficiently improved, while if it exceeds 30% by weight, the resin composition becomes hard and the extrusion moldability is good, but the elasticity of the molded product is poor. , Lacks practicality.

The vinyl chloride-based resin composition produced by the method of the present invention may also be used for the purpose of smooth kneading and molding.
Fillers may be added. The filler has a favorable effect of absorbing an excessive amount of the plasticizer, but when added in an excessively large amount, the concealing property becomes large, and it is desirable to avoid adding too much. The filler should be added in an amount up to 150 parts by weight, preferably 100 parts by weight or less, based on 100 parts by weight of the vinyl chloride resin.
It is also preferable from the viewpoint of economy to add the compound within a range that does not impair moldability. As filler, carbon black,
Examples include calcium carbonate, titanium oxide, talc, aluminum hydroxide, magnesium hydroxide, hydrotalcite, clay, silica, and white carbon.

The vinyl chloride resin composition according to the method of the present invention may further contain, if necessary, known components such as a flame retardant, a stabilizer, a lubricant, an antioxidant, an ultraviolet ray inhibitor, in addition to the above-mentioned components.
Various additives such as a foaming agent and a colorant can be added in amounts that do not deteriorate the physical properties of the composition. Examples of the flame retardant include antimony trioxide, zinc borate, barium metaborate, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, dawsonite, calcium aluminate, red phosphorus, zinc stannate, zinc hydroxystannate, and molybdate And the like.

The vinyl chloride resin composition according to the method of the present invention is produced, for example, as follows. 1. Vinyl chloride resin, stabilizer, plasticizer if necessary,
A method in which predetermined amounts of an acrylic resin and other various additives are previously mixed or dry-blended with a high-speed mixer to prepare a uniform mixture, and then mixed or kneaded together with the phosphorescent phosphor. At this time, a) a method in which a phosphorescent phosphor is added to the homogeneous mixture, the mixture is lightly stirred, and then a kneading operation is performed. b) A method in which the homogeneous mixture and the phosphorescent phosphor are added together during the kneading operation to perform the kneading operation. There is.

The mixer for preparing the homogeneous mixture is not particularly limited as long as it can be blended substantially uniformly, but a so-called high-speed mixer is used from the viewpoint of productivity. The high-speed mixer is a mixer used for dry blending of vinyl chloride resin and the like, and has a special rotor with a twisted wing at the bottom, and when horizontally rotated at a high speed of 500 to 1800 rpm, The powder material undergoes vigorous vortex and convection motions and is mixed in a short time. It is preferable that a baffle plate is provided in the tank to facilitate mixing, the temperature of the material is directly measured by a thermocouple, and heating and cooling can be performed by a jacket. Specifically, Henschel mixers or super mixers (Henschel AG-Germany) are commercially available.

2. A method in which a predetermined amount of a vinyl chloride resin, a phosphorescent phosphor and a stabilizer, and, if necessary, a plasticizer, an acrylic resin, a filler and other additives are blended in a low-speed mixer and then kneaded. Is mentioned. The low-speed mixer used in the latter method 2 is, for example, a material having a high shear stress on a material to be mixed such as a ball mill, a pebble mill, a tumble mixer, a ribbon mixer (ribbon blender), a planetary mixer, a changeable mixer, and a crusher. Is a type of mixer that does not give

The kneader used for kneading is preferably an internal mixer or an extruder. Examples of the internal mixer include a Banbury mixer, an intensive mixer,
It is commercially available under trade names such as a closed automatic mixer, an intermix, a pressurized kneader, a continuous mixer, and a transfer mix. The extruder may be a single screw extruder or a twin screw extruder. Of course, Niddar,
Kneading with an open roll or the like is acceptable. The temperature of the kneading resin is desirably 175 ° C or lower, preferably 165 ° C or lower. The vinyl chloride resin composition may be used as it is as a dry blend, but is usually produced as pellets and subjected to various molding methods.

The vinyl chloride resin composition produced by the method of the present invention can be used to form a film or sheet by various molding methods such as calendering, extrusion molding, injection molding, coextrusion molding, insert injection molding, and simultaneous injection molding. It is formed into irregularly shaped articles and the like, and is effectively used, for example, for vehicle interior / exterior material parts, architectural interior / exterior material parts, electric equipment parts, advertising panels, toys and the like. In particular, it is highly useful as equipment, appliances, stair handrails, safety signboards, guidance signboards, hallway signboards, display boards, etc. used at night.

[0028]

EXAMPLES Next, the vinyl chloride resin composition of the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless departing from the gist thereof. Examples 1 to 15 and Comparative Examples 1 to 6 Vinyl chloride resin, phosphorescent phosphor, stabilizer and other various additives shown in Table 1 in amounts shown in Table 1 and Table 2 (parts by weight) Was charged into a ribbon mixer, which is a low-speed mixer, and mixed.
(0 ° C.) for 3 minutes to prepare a uniform composition. The composition was formed into a sheet by two rolls, and the sheet was further pressed at a temperature of 160 ° C. for 2 minutes by a press forming machine to prepare a sheet having a thickness of 1 mm. The composition was evaluated as follows, and the results are shown in Tables 1 and 2.

In the examples, 0.005 mol% of europium and 0.1% of dysprosium were used as the phosphorescent phosphor.
Strontium aluminate (hereinafter referred to as phosphor A) activated at 005 mol% was used, and zinc sulfide (hereinafter referred to as phosphor B) activated with copper was used as a phosphorescent phosphor in a comparative example.

[0030]

[Table 1] Evaluation method; Roll processability: The degree of cohesion of the resin when the composition mixed by the ribbon mixer was put into two rolls was visually judged. ○ good × bad Sheet coloring: The degree of coloring of a pressed sheet having a thickness of 1 mm was visually determined. ○ No coloring (yellow green fluorescence) × Brown or black coloring (poor fluorescence) Sheet persistence: After storing a 1 mm thick pressed sheet in a dark place for 24 hours, irradiate sunlight (550 lux) for 1 hour, and then Luminescence in a dark place was visually observed. 1 Afterglow after 1 hour 2 Afterglow even after 30 minutes 3 No afterglow after 30 minutes 4 No afterglow after 10 minutes

[0031]

[Table 2] The following ingredients were used as compounding ingredients other than the phosphors described in Tables 1 and 2. Vinyl chloride resin: PVC-a average polymerization degree 2350 (manufactured by Mitsubishi Chemical Corporation) PVC-b average polymerization degree 700 (manufactured by Mitsubishi Chemical Corporation) Plasticizer: DINP diisononyl phthalate D623 adipic acid-based polyester (Mw1800, manufactured by Mitsubishi Chemical Corporation) Soybean oil Epoxidized soybean oil Stabilizer: Zn-St zinc stearate Pb-St lead stearate Ba-Zn Ba-Zn composite stabilizer (M-RuP14, manufactured by Asahi Denka) Mg-Zn Mg-Zn composite stabilizer (NL-120, manufactured by Mizusawa Chemical Co., Ltd.) DMSn dimethyltin mercaptide (TM181, manufactured by Katsuta Kabushiki Kaisha) Ts-GM Tribasic lead sulfate Ba-St Barium stearate Ca-St Calcium stearate Mg-Al Synthetic hydrotalcite (Alkaline (Mizer 1, Kyowa Chemical Co., Ltd.) UV absorber: benzophenone UV absorber Acrylic resin: Methacryl Methyl luate copolymer (METABLEN P-551, manufactured by Mitsubishi Rayon Co., Ltd.) Filler: calcium carbonate Pigment: ultramarine (Ts7954, manufactured by Dainippon Ink)

[0032]

[Table 3]

[0033]

[Table 4]

Example 16 PVC-a 100 parts by weight, Mg-Zn 2 parts by weight, DIN
80 parts by weight of P and 2 parts by weight of soybean oil were charged into a Henschel mixer as a high-speed mixer, and mixed until the resin temperature reached 105 ° C. to prepare a uniform dry blend. 20 parts by weight of phosphor A was added to this dry blend and stirred for 30 seconds to obtain a vinyl chloride resin composition of the present invention. The composition was kneaded with a Banbury mixer at a rotation speed of 60 rpm to a resin temperature of 160 ° C. and then pelletized. This pellet was formed into a sheet with two rolls having a surface temperature of 160 ° C. in the same manner as in Example 1, and then press-molded to form a sheet having a thickness of 1 mm. did. The results are shown in Table-3.

The color difference was evaluated by the following test method. In Example 16, the components except phosphor A were mixed in a glass beaker, and then dried up using a microwave oven. The phosphor A was added thereto, and the mixture was uniformly stirred with a glass rod. Then, the mixture was directly press-formed to form a sheet. Since this sheet does not collide with a metal during the manufacturing process, the surface color difference of the vinyl chloride resin composition sheet obtained according to the present invention is measured using Aucolor VP-1 manufactured by Kurabo Industries Co., Ltd. as a standard. did.

Example 17 The vinyl chloride resin composition prepared in Example 16 was extruded (temperature conditions: C1: 140 ° C., C2: 150 ° C., C3:
160 ° C., D: 160 ° C.)
The composition was evaluated in the same manner as described above, and the results are shown in Table 3. Example 18 The dry blend material and the phosphor A before charging the phosphor A prepared in the example 16 were directly charged into a Banbury mixer and kneaded at a rotation speed of 60 rpm to a resin temperature of 160 ° C. to produce pellets. The composition was evaluated in the same manner as in Example 16, and the results are shown in Table 3.

Example 19 All the components of Example 16 were charged into a ribbon mixer and mixed up to a resin temperature of 105 ° C. to prepare a dry blend. The dry blend was kneaded with a Banbury mixer at a rotation speed of 60 rpm to a resin temperature of 160 ° C., and then pelletized. The composition was evaluated in the same manner as in Example 16, and the results are shown in Table 3. Example 20 A dry blend was prepared by mixing the components of Example 16 except for phosphor A to a resin temperature of 105 ° C. using a ribbon mixer, and the blend and phosphor A were directly charged into a Banbury mixer. The mixture was kneaded to a resin temperature of 160 ° C. to form pellets. The pellets were evaluated for quality in the same manner as in Example 16, and the results are shown in Table 3.

Comparative Example 7 A composition was prepared and evaluated for quality in the same manner as in Example 19 except that the Henschel mixer was used instead of the ribbon mixer of Example 19, and the results are shown in Table 3. Comparative Example 8 The dry blend product mixed in the Henschel mixer in Comparative Example 7 was extruded using an extruder under the extrusion conditions in Example 17 and pelletized. The quality of the pellets was evaluated, and the results are shown in Table 3.

[0039]

[Table 5]

[0040]

According to the present invention, the phosphorescent phosphor containing a metal aluminate as a phosphor matrix for use in the method of the present invention can be prepared by selecting a specific stabilizer and by adding a phosphorescent phosphor at a specific time during the production of the composition. By adjusting the production method or by adjusting the production method, the produced vinyl chloride resin composition can be kneaded without causing discoloration of the phosphorescent phosphor and without impairing the fluorescence. And the vinyl chloride resin composition is excellent in discoloration resistance and molding processability,
A resin molded article molded from the composition emits fluorescence over a long period of time and can be used as a raw material for various devices, instruments, devices, decorative materials, and the like particularly used in the dark or at night.

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[Procedure amendment]

[Submission date] July 23, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

The weight average degree of polymerization of the vinyl chloride resin based on JIS K6721 is in the range of 400 to 10,000, preferably in the range of 600 to 4500. If the average degree of polymerization is less than 400 , the weather resistance tends to be poor, and if it exceeds 10,000, kneading and molding become difficult.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

[0029] Incidentally, the strontium aluminate which is activated with a <br/> Yuuropiu arm及 beauty Jisupuroshiu beam as in phosphorescent phosphor in Example (hereinafter referred to as phosphor A), as in the phosphorescent phosphor in Comparative Example Zinc sulfide activated with copper (hereinafter referred to as phosphor B) was used.

Claims (12)

[Claims] 1. A vinyl chloride resin comprising at least one of a phosphorescent phosphor comprising a metal compound represented by the following general formula (1) and an activator and a metal element selected from zinc, tin or lead. In the method for producing a vinyl chloride resin composition containing a stabilizer containing the same, the vinyl chloride resin and the stabilizer are preliminarily mixed to form a uniform mixture, and then the mixture is mixed with the phosphorescent phosphor. Or a method for producing a vinyl chloride resin composition, which comprises kneading. General formula (1); MAl ₂ O ₄ (wherein, M represents at least one metal element selected from magnesium, calcium, strontium, and barium) 2. The method for producing a vinyl chloride resin composition according to claim 1, which is a homogeneous mixture obtained by dry blending a plasticizer. 3. The method for producing a vinyl chloride resin composition according to claim 1, which is a homogeneous mixture containing an acrylic resin. 4. The method for producing a vinyl chloride resin composition according to claim 1, which is a homogeneous mixture containing a filler. 5. The method for producing a vinyl chloride resin composition according to claim 1, wherein the preparation of the homogeneous mixture is performed by a high-speed mixer. 6. A phosphorescent phosphor is added during kneading.
A method for producing the vinyl chloride resin composition according to any one of claims 1 to 5. 7. A vinyl chloride resin containing at least one of a phosphorescent phosphor comprising a metal compound represented by the following general formula (1) and an activator and a metal element selected from zinc, tin or lead. A method for producing a vinyl chloride resin composition containing a stabilizer comprising: mixing the above components together with a low-speed mixer, or kneading the mixture further, wherein the mixture is further kneaded. Manufacturing method. General formula (1); MAl ₂ O ₄ (wherein, M represents at least one metal element selected from magnesium, calcium, strontium, and barium) 8. The method for producing a vinyl chloride resin composition according to claim 1, wherein the kneading is performed by an internal mixer or an extruder. 9. The content of the phosphorescent phosphor and the heat stabilizer is 5 to 200 parts by weight per 100 parts by weight of the vinyl chloride resin.
2 parts by weight and from 0.05 to 20 parts by weight.
A method for producing the vinyl chloride resin composition according to any one of claims 1 to 8. 10. The method for producing a vinyl chloride resin composition according to claim 1, wherein the activator is at least one selected from the group consisting of rare earth elements, manganese, tin and bismuth. 11. An activator selected from the group consisting of europium and a co-activator selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin and bismuth. The method for producing a vinyl chloride resin composition according to any one of claims 1 to 10, wherein the composition is at least one kind. 12. A vinyl chloride resin having a weight average polymerization degree of 4
12. The method according to claim 1, wherein the range is from 00 to 10,000.
A method for producing the vinyl chloride resin composition according to any one of the above items.