JPS5943044B2 - Manufacturing method for molded products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a molded article by calendering, extrusion molding, or injection molding an active energy ray-curable polyvinyl chloride resin composition.

Specifically, the present invention relates to a non-sol type polyvinyl chloride resin, a reactive plasticizer having at least one aromatic ring, a photosensitizer, a stabilizer, and, if necessary, a polymerization inhibitor. The present invention relates to a method for producing a molded article by calender molding, extrusion molding, or injection molding a vinyl chloride resin composition. Polyvinyl chloride resin (hereinafter abbreviated as PVC) is mostly molded through heat processing such as calendar processing, extrusion processing, and injection molding, and is used to produce films, sheets, belts, etc.
It is used in a wide range of fields such as electric wires. In recent years, there has been a demand for improvements in the heat resistance and mechanical strength of PVC products. Electron beam bridges, etc. are being studied and put into practical use. In addition to these methods, reactive plasticizers can also be used in PVC.
Studies are underway to improve heat resistance and mechanical strength by blending them into organic peroxides and crosslinking and curing them by heating, irradiation with active energy rays, etc. in the presence of organic peroxides. Products obtained by blending such reactive plasticizers have improved heat resistance such as heat deformation resistance and cigarette mark resistance, and mechanical strength such as hardness and tensile strength, so they are attracting attention for application as top coat layers of flooring materials. has been done.

In particular, the method of cross-linking and curing by irradiation with active energy rays does not cause gelation of the reactive plasticizer compared to the method of using organic peroxides as a curing catalyst, resulting in products with transparent and uniform skin. This is useful because it allows you to However, this method of irradiation with active energy rays has the disadvantage that not only does PVC partially decompose and coloration occurs after irradiation, but also that coloration of the product is significantly accelerated during heating during secondary processing. That is, when a PVC sheet crosslinked by active energy ray irradiation is heated to around 150'C and press-fused as a top coat layer of flooring material,
The PVC sheets turn yellow, and in some cases turn brown, and have the disadvantage of significantly detracting from the commercial value of products, especially fashion floors used in department stores, coffee shops, and home kitchens. The inventors have discovered that PVC without such drawbacks
As a result of intensive studies on the method for manufacturing molded products using the composition, we found that by incorporating a reactive plasticizer with at least one aromatic ring, such coloring during molding can be eliminated and weather resistance can be improved. They discovered what could be done and completed the present invention.

That is, the present invention comprises A) PVC) (B) a reactive plasticizer having at least one aromatic ring; (C) a photosensitizer; The present invention provides a method for producing a molded article, which comprises performing calendar molding, extrusion molding, or injection molding of a non-sol type PVC composition comprising the present invention.

The present invention further improves the composition by adding a tin stabilizer, a phosphorous acid ester, and a non-coloring antioxidant to the above composition.

The present invention also provides a method for producing a molded article using a non-sol type PVC composition in combination with at least one of the above. PVC used in the present invention is a homopolymer of vinyl chloride with an average degree of polymerization of 700 to 4,000 or a monomer copolymerizable with vinyl chloride, such as vinyl acetate, acrylonitrile, styrene, (meth)acrylic acid ester, ethylene, propylene. , butylene, etc., alone or in mixtures.

[Mine: In the present invention, such PVC can be mixed with other polymers.

Any other polymer can be used as long as it is compatible with PVC, but an elastomer that can impart flexibility to the composition is preferred. Examples of such elastomers include natural rubber, nitrile rubber, and styrene rubber.
Butadiene rubber, acrylonitrile-butadiene rubber,
Examples include synthetic rubbers such as chloroprene rubber and acrylic rubber, chlorinated polyethylene, ethylene-vinyl acetate copolymers, and ethylene-vinyl acetate-vinyl chloride graft copolymers. When this elastomer is blended with PVC, the amount is usually PVCIOO parts by weight (hereinafter referred to as
1 to 30 parts, preferably 3 to 10 parts. The reactive plasticizer used in the present invention has at least one aromatic ring in its structure and has good compatibility with PVC.

Specifically, a polyfunctional acrylic oligomer obtained from an alkylene oxide adduct of bisphenol A or bisphenol F and acrylic acid or methacrylic acid, such as the formula (I) (where R and R, each represents a hydrogen atom or a methyl group, and m and n represent integers of 2 to 3 and 1 to 10, respectively.

) (...) A polyfunctional alcohol obtained from a polyhydric alcohol such as butylene glycol, trimethylolpropane, pentaerythritol, etc., and an aromatic monocarboxylic acid such as benzoic acid, paratertiary butylbenzoic acid, and acrylic acid or methacrylic acid. Acrylic oligomer 1, formula () (wherein R2 is a hydrogen atom or a methyl group; R3 is a dihydric or higher alcohol residue having 2 to 10 carbon atoms, or an alkylene oxide having 2 to 4 carbon atoms in the alcohol) Added polyether polyol residue; R4 has 1 to 1 carbon atoms
Indicates a phenyl group substituted with 0 alkyl groups or unsubstituted.

n is a number from 0.1 to 5.9 and represents an average value. x is an integer of 2 or more. Also, x-n is always greater than 1. ) () Aromatic dibasic acids such as phthalic anhydride, isophthalic acid, and terephthalic acid as shown in the formula () and, if necessary, a small amount of aromatic polybasic acids such as trimellitic anhydride and trimesic acid, and ethylene glycol, propylene glycol, butylene glycol, Pentanediol. A polyfunctional acrylic oligomer obtained from a glycol such as hexanediol or octanediol and an unsaturated monobasic acid such as acrylic acid or methacrylic acid (formula 9 (in the formula, R5 is a hydrogen atom or a methyl group, R6 is 2 to alkylene group having 10 carbon atoms,
n is an integer of 1 to 10, and Ar is a divalent aromatic group.

) Aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane 4,4'-diisocyanate, and glycols such as ethylene glycol, butylene glycol, hexanediol, and octanediol, and optionally a carbon number of 2 to 10. A polyether polyol in which an alkylene oxide having 2 to 4 carbon atoms is added to a divalent or higher alcohol, and a hydroxyl compound such as 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, etc. A polyfunctional acrylic oligomer obtained from acrylates - 0V formula (wherein R7, R, O are hydrogen or methyl groups, R2 is 2-
alkylene group having 3 carbon atoms, R3 is an alkylene group having 2 to 10 carbon atoms, molecular weight 200 to 100
00 polyethylene glycol or polypropylene glycol residue, n is an integer of 0 to 10, and Ar is an aromatic group.

) Other examples include aromatic unsaturated esters such as diallyl phthalate, triallyl trimellitate, and trimethallyl trimellitate.

In addition, a reactive plasticizer having no aromatic ring, which is usually used in PVC, can of course also be used in combination.

However, it is necessary to keep the blending amount within a range that does not affect heat resistance, and specifically, it is desirable to use it in an amount of 50% by weight or less based on the total amount of reactive plasticizer. The photosensitizer used in the present invention is one that facilitates the cross-linking reaction of a reactive plasticizer by photoexcitation upon irradiation with active energy rays, and examples thereof include benzoyl, α-methylbenzoyl, α-allylbenzoyl, and benzoin. Methyl ether, benzoin isopropyl ether, benzoin-sec-butyl ether, acetophenone, benzophenone, p-prombenzophenone, 4,4'-tetramethyldiaminobenzophenone, diphenyl disulfide, tetraethylthiural disulfide, decyl Examples include allyl sulfide, decylthiobenzoate, benzyl acetyl, uranyl nitrate, eosin or naonine. ．． Others such as trinitroaniline, nitronaphthalene,
Aromatic nitro compounds such as 5-nitroacenaphthene, 2-nitrofluorene, and picramide, quinones such as naphthoquinone, anthraquinone, and 2,3-diphenylanthraquinone, anthrone, pyrylium salts, etc. are used in combination with the above-mentioned photosensitizers. It is preferable to use it as it is more effective. Among these, benzoin compounds are preferred, and penzoin isopropyl ether is particularly preferred. The stabilizer used in the present invention can be any stabilizer that is normally used for PVC, such as white lead, tribasic lead sulfate,
Lead salts such as tribasic lead maleate and silicate: lead, cadmium, barium, zinc, calcium, etc. and stearic acid,
Examples include metal soaps containing lauric acid, ricinoleic acid, naphthenic acid, etc.; tin-based stabilizers, phosphorous acid esters, etc., which will be described later.

Particularly preferred are tin stabilizers and phosphite esters. Furthermore, non-coloring antioxidants can also be used in place of stabilizers to provide even better results. The tin stabilizer mentioned above has the general formula R'PSnY4-p (wherein R' is alkyl having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, heptyl, hexyl, pentyl, octyl, etc., and Y is It is a monovalent residue of lauric acid, maleic acid, and mercaptan compounds.

Further, p is an integer of 1 to 3. It is expressed as Specifically, for example, monobutyltin trimethyl maleate, monobutyltin trioctyl maleate, dibutyltin dilaurate, dibutyltin laurate methyl maleate, dibutyltin dioleyl maleate, dibutyltin dimethyl maleate, dibutyltin maleate, dibutyltin methoxymethyl maleate, dibutyltin. Laurates such as dioctyl maleate, maleates, methyltin sulfide, n-butyltin sulfide, n-octyltin sulfide, methyltin tris (n-octylthioglycolate), n-butyltin tris (isooctylthioglycolate) ), n-butyltin tris(3,4,5-
trimethyl thiomalate), n-octyltin tris(
cyclohexyl-3-mercaptopropionate), ethyltin tris (ethyl-2-mercaptomyristate), isopropyltin tris (methoxyethyl-3-mercaptopropionate), n-propyltin tris (
methyl-2-mercaptobenzoate), methyltintrisoctylmercaptite, isoamyltintris(
Tetrahydrofurfuryl-3-mercaptopropionate), mono-n-butyltin monoisooctylthioglycolate sulfide, mono-n-octyltin monocyclohexylthioglycolate sulfide, dimethyltin bis(isooctylthioglycolate) , dibutyltinbis(isooctylglycolate), di-n-octyltinbis(isooctylthioglycolate), and other sulfur-containing organotin stabilizers. In particular, mercaptite-based tin stabilizers such as dimethyltinbis(isooctylthioglycolate) and dibutyltinbis(isooctylthioglycolate) are most effective in preventing coloration during heating. Other metal soaps, lead-based stabilizers, and the like cannot be used because they often reduce transparency and other effects, but those that do not reduce such effects can of course be used. Examples of the above phosphites include diethyl phosphite, dibutyl phosphite, dioctyl phosphite, diphenylnonylphenyl phosphite, diphenylisodecyl phosphite, trimethyl phosphite, tricresyl phosphite, and triphenyl phosphite. Phosphite, tris (nonylphenyl) phosphite, trisooctyl phosphite, trilauryl phosphite, triisodecyl phosphite, triotadecyl phosphite, trilauryl trithiophosphite, trischloroethyl phosphite, dibutylhydrodiene phosphite, etc. It will be done.

In addition, non-coloring antioxidants are usually colorless among the antioxidants used and do not color the PVC composition. Specifically, as phenolic antioxidants,
Hydroquinone series such as 2,5-di-1(t-amyl)hydroquinone, 2,5-di-1(t-butyl)hydroquinone, hydroquinone monomethyl ether, 1-oxy-3-methyl-4-isopropylbenzene, 2,6 -di-t-butylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol Monophenols such as n-butylphenol, 4,4'-dihydroxydiphenyl, 2,2-methylene-bis-(4-methyl-6
-cyclohexylphenol), 2,2'-methylene-bis-(6-α-methyl-benzyl-P-cresol), 1,1-bis-(4-hydroxyphenyl)-cyclohexane, hindered bisphenol, Tris One (2
-methyl-4-hydroxy-5-t-butylphenyl)
Bis-1, Tris-1, polyphenols such as butane, 4,
4! Thiobisphenol type antioxidants such as -thiobis-(6-t-butyl-4-methylphenol), non-coloring amine type antioxidants such as N,N'-di-10-tolylethylenediamine, N,N'-di-1 2-naphthyl-P-phenylenediamine, others include dilaurylthiodipropionate, distearylthiodipropionate, distearyl-β,β7-thiodibutyrate, 2-mercaptobenzimidazole, tris(nonylphenyl)phosphite, tris (mono- and dinonylphenyl) phosphites, alkylaryl phosphites, and the like. Such tin-based stabilizers, phosphite esters, and non-coloring antioxidants can be used alone or in combination, but most preferably tin-based stabilizers are used. Compositions used in the present invention In addition to the above-mentioned components, a polymerization inhibitor may be added if necessary.

Examples of such polymerization inhibitors include commonly used ones such as hydroquinone, benzoquinone, phenothiazine, hydroquinone monomethyl ether, t-butylhydroquinone, and methylhydroquinone. Furthermore, dyes and non-reactive plasticizers may be added to the composition used in the present invention, if necessary. In addition, non-reactive plasticizer,
So-called dioctyl phthalate, dibutyl phthalate, dibutyl lauryl phthalate, diheptyl phthalate, etc. have the advantage of imparting flexibility to the composition and at the same time improving coloration upon irradiation with active energy rays. PVClO
It is used in an amount of 1 to 15 parts based on O parts. The amount of the reactive plasticizer in the composition used in the present invention may be any amount as long as it achieves the effects of the present invention.
Usually 3 to 70 parts per part of PVClOO, preferably 1
It is 0 to 50 parts.

If the amount of the reactive plasticizer is less than 3 parts, the heat resistance after curing will be insufficient, and if it exceeds 70 parts, the silver composition after curing tends to become too rigid. The content of photosensitizer in the composition of the present invention is related to the amount of reactive plasticizer, and is usually from 0.001 to 1% based on the weight of the reactive plasticizer.
0 weight is 70.

Of course, it is acceptable to deviate from this amount as long as the effects of the present invention can be achieved. Further, the amount of stabilizers, particularly tin stabilizers, phosphite esters, and non-coloring antioxidants in the composition of the present invention is usually 0.00% relative to parts of PVClOO.
0.5 to 5 parts, preferably 0.5 to 2 parts.

Even when two or more such stabilizers are used, the above amount JU
used in

If the amount is less than 0.05 parts, the effect of preventing discoloration during heat treatment of the composition will not be achieved, and if it is more than 5 parts, the stickiness to the molding machine will increase, which is undesirable. When the PVC composition is highly sticky, a known lubricant such as higher alcohol, stearic acid, glycerin monostearate, ethylene bisstearamide, polyethylene glycol, liquid paraffin, polyethylene wax, etc. may be added to 0 parts of PVClOO. , the tackiness can be reduced by adding 1 to 1 part of the polymerization inhibitor to the composition of the present invention. is related to the amount of reactive plasticizer, usually 5% by weight based on the weight of the reactive plasticizer.
It is used below, preferably at 2% by weight or less.

The composition containing the above-mentioned components is not a usual sol-type composition, but is heat-molded by calender molding, extrusion molding, injection molding, or the like.

The heating temperature at this time is usually 150 to 230°C. Next, the thermoformed PVC molded article is cured by irradiation with active energy rays.

The active energy rays at this time include α rays, β rays, γ rays,
Examples include ultraviolet rays, high frequencies, etc., especially 1800~
Actinic radiation having a wavelength of 7000 is preferred. Examples of the light source that generates actinic rays having this wavelength include carbon arc lamps, mercury vapor lamps, ultraviolet lamps, tungsten lamps, incandescent lamps, xenon lamps, argon glow lamps, photographic irradiation lamps, and sunlight. Furthermore, after irradiation with active energy rays, the molded product obtained in the present invention undergoes secondary processing such as press fusion, whereby the polymerization reaction of the remaining double bonds of the reactive plasticizer progresses, improving the degree of crosslinking and hardening. obtain.

At this time, heating at 150° C. or higher is particularly effective. The resulting PVC molded product is cross-linked and cured, resulting in excellent surface hardness, little discoloration, and good transparency, abrasion resistance, and cigarette mark resistance.

The reason why the molded product according to the present invention has such an excellent effect is not clear in detail, but the reactive plasticizer crosslinks and forms a network at the same time as it polymerizes when irradiated with active energy rays, and PVC is uniformly filled between the networks. This is thought to be due to the fact that The PVC molded article according to the present invention can be applied to fields where the use of reactive plasticizers has heretofore been restricted, and has great industrial value.
For example, sheets of molded material can be laminated as the top layer of flooring materials, especially fashion floors, to provide aesthetically pleasing flooring materials with excellent cigarette mark resistance, as well as wall coverings, leather, heat-resistant materials, etc. It is suitable as a molding material for hoses, oil seals, packing, heat-resistant wire coating materials, decorative boards, etc. Of course, it can also be used for other purposes. Next, a typical embodiment of applying the PVC composition of the present invention to a fashion floor will be shown.

10.3~2.0m77! A subbing layer is coated on a thick base material, for example, by coating PVC sol to a thickness of 0.2 to 3.0 mm.
The mixture was allowed to semi-gel at 0°C, and then the sheet with the printed pattern was adhered.

The PVC composition of the present invention is then fused thereon at 150° C. to obtain a fashion floor with excellent cigarette mark resistance. A base material with a thickness of 20.3 to 2.0 mm is coated with a subbing layer containing a foaming agent.
It is coated to a thickness of 3.0 mm, semi-gelled at 120°C, printed with a printed pattern, and then foamed and embossed at 200°C.

The PVC composition of the present invention is fused thereon at 150°C to obtain a fashion floor with excellent cigarette mark resistance.

Such a fashion floor will be explained with reference to the drawings.

That is, FIG. 1 is a cross-sectional view of a fabric floor, which is made of asbestos and glass fiber-filled P.
Foamed or non-foamed, non-embossed PVCl natural rubber, synthetic rubber, ethylene monovinyl acetate copolymer, polyurethane or urea foam on a base material 1 such as VCl linen felt, cotton cloth, non-woven fabric, PVC, PVC foam, etc. , a subbing layer 2 of phenol foam or the like is coated, a printed layer 3 of a printed or printed sheet is placed thereon, and the PVC composition of the present invention is further coated thereon. FIG. 2 is a sectional view of the fashion floor in which the undercoat layer 2 in FIG. 1 is embossed. Figure 3 shows an undercoat layer 2 on top of a base material 1.
FIG. 2 is a sectional view of a fashion floor partially coated with PVC composition 4 according to the present invention. Fourth
The figure shows a substrate 1 comprising chips 5 of natural rubber, crosslinked or non-crosslinked PVCl, synthetic rubber, ethylene monovinyl acetate copolymer, polyurethane, cork, etc., embedded in the soil and partially exposed. FIG. 2 is a sectional view of a fashion floor coated with an undercoat layer 2 and further coated with the PVC composition of the present invention. FIG. 5 shows a substrate 1 coated with an undercoat layer 2,
PVC clear layer 6 with chips 5 embedded thereon
FIG. 2 is a sectional view of a fashion floor coated with PVC composition 4 and further coated with PVC composition 4 according to the present invention. Further, a typical embodiment of applying the PVC composition of the present invention to a wall covering material is shown. A subbing layer is coated on one substrate, such as PVC.
A 0.05 to 0.3 mm thick sol is applied, semi-gelled at 120°C, then a sheet with a printed pattern is adhered thereon, and the PVC composition of the present invention is applied on top of it.
By fusing at 50°C, a wall covering material with excellent heat resistance is obtained.

2. Cover the substrate with an undercoat layer, 1. For example, apply a foamed PVC sol to a thickness of 0.05 to 0.3 mm, and semi-gel it with 120C. 1. Then, print or print a printed pattern on it. After adhering the sheet, it was foamed and embossed at 20"C, and 1% of the PVC composition of the present invention was applied on top of it.
By fusing at 50°C, a wall covering material with excellent heat resistance is obtained.

This wall covering material will be explained using drawings.

That is, FIG. 6 shows foamed or non-foamed, unembossed PVCl natural rubber, synthetic rubber, ethylene monovinyl acetate copolymer, polyurethane or urea on a substrate 7 such as paper, PVC board, plywood, cloth, asbestos, etc. A wall covering material comprising a subbing layer 8 such as a foam or phenol foam, a printed layer 9 of a printed or printed sheet placed thereon, and a PVC composition according to the present invention further coated thereon. FIG. Further, FIG. 7 shows a substrate 7 covered with a foamed or non-foamed embossed subbing layer 8, a printed layer 9 placed on top of that, and a PVC composition of the present invention further coated thereon. FIG. Furthermore, a typical embodiment of applying the PVC composition of the present invention to leather is shown.

1. A subbing layer is coated on a cloth, 0.2 to 3.0 mm of, for example, PVC sol containing a foaming agent is coated, and foaming and gelling is carried out at 200°C. 1. The PVC composition of the present invention is coated on top of it at 150°C.
to obtain leather with excellent heat resistance.

2. Cover the cloth with an undercoat layer, 1. Cover the cloth with PVC sol containing a foaming agent for 0.2 to 3.0 minutes, foam and gel at 200°C. The PVC composition of the invention is fused at 150°C to obtain leather with excellent heat resistance.

Such a laser will be explained using drawings. That is, FIG. 8 is a cross-sectional view of a leather obtained by coating a cloth 11 with an undercoat layer 12 of foamed or non-foamed PVC without wrinkles, and further coating the PVC composition 13 of the present invention on top of this. It is. Also, the 9th
The figure shows foamed or non-foamed PVC with wrinkles on the cloth 11.
The undercoat layer 12 of the present invention is coated, and the PVC of the present invention
FIG. 2 is a cross-sectional view of a leather coated with Composition 13. Furthermore, 〇4, which shows a typical embodiment when the PVC composition of the present invention is applied to a decorative board, is coated with an adhesive, such as vinyl acetate resin emulsion, acrylic resin emulsion, synthetic rubber latex, unsaturated polyester, or epoxy resin. etc., and place a sheet with a printed pattern on it,
Then, the PVC composition of the present invention is fused thereon at 150°C.

Thereafter, after press bonding, active energy rays are irradiated to obtain a decorative board. 2 In the above method, the PV of the present invention
The C composition is irradiated with active energy rays in advance, and the composition is fused at 150° C. and then press bonded to obtain a decorative board.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited only to the Examples.

Examples 1 to 16 and Comparative Examples 1 to 5 Each of the formulations listed in Table 1 was kneaded for 17 minutes using a calendar roll (two rolls) to give a thickness of 0.
I got 3 seats.

Next, each sheet was heated using a high-pressure mercury lamp (80
Irradiation was performed using two W/C7rL ultraviolet (UV) lamps at a distance of 15 from the light source (17711 belt speed of 20 m/min). Each sheet obtained was tested for cigarette mark resistance, heat coloring resistance, heat distortion temperature, tensile strength, elongation, and Brabender's torque stability. The result is the first
Shown in the table. Each physical property shown in Table 1 was determined by the following method.

<Cigarette mark resistance> Take a commercially available lit cigarette (Seven Star, manufactured by Japan Monopoly Corporation) that has burnt more than 10 mm from the tip and has not progressed to within 30 skins from the other end, remove the ashes well, and remove the ash from the sample. Place it on the seat surface and immediately rub it in with the sole of your shoe and observe the surface condition of the seat surface, the degree of destruction, and how the ash is attached.

Heat resistant coloring property> Heat to 180°C in a gear oven and suppress the time it takes for the specimen to turn brown.

<Weather resistance> Observe the discoloration of the specimen after 100 hours of exposure in a sash yarn type weatherometer.

<Heat distortion temperature> Measured according to JISK-6919.

Tensile strength and elongation> Tested using a No. 3 tamper with an Instron type tester,
Tensile strength and elongation are measured by tensile conditions of 200 mm/min at 3°C and 50°C.

Brabender's best torque stability>Brabender's plastic corder was filled with 609% of uncrosslinked PVC composition, and the jacket temperature was 18'C, 6Orpm.
Rotation was started at , and it was observed whether or not there was an increase in torque for 15 minutes.

Examples 17-28 Each of the formulations listed in Table 2 was treated in the same manner as in Example 1 to obtain sheets.

Next, each sheet was irradiated two to four times under the same UV irradiation conditions as in Example 1, as appropriate. The physical properties of the obtained sheet are shown in Table 2. Examples 29-31 Each of the formulations listed in Table 3 was treated in the same manner as in Example 1 to obtain sheets.

Next, each sheet was irradiated under the same UV irradiation conditions as in Example 1. Furthermore, the obtained sheet was coated with 0.5 mm of PVC sol on 1.0 m 1 L thick asbestos.
The mixture was semi-gelatinized at 0°C, and then press-fused onto a printed pattern at 150°C for 30 minutes to obtain a fashion floor. The resulting fashion floor was tested for cigarette mark resistance. The results are shown in Table 3.

[Brief explanation of the drawing]

Figures 1, 2, 3, 4 and 5 are cross-sectional views of fashion floors of different configurations. 6 and 7 are cross-sectional views of wall coverings of different shapes, respectively. Further, FIGS. 8 and 9 are cross-sectional views of lasers of different shapes. 1,7...
・Substrate, 2, 8, 12... Undercoat layer, 3, 9...
... Print layer, 4, 10, 13 ... PVC composition of the present invention, 5 ... Chip, 6 ...
... Clear layer, 11... Cloth.

Claims (1)

[Claims] 1 (A) polyvinyl chloride resin, (B) a reactive plasticizer having at least one aromatic ring, (C) a photosensitizer, (D
) A method for producing a molded article, which comprises calendering, extrusion molding, or injection molding a non-sol type polyvinyl chloride resin composition containing a stabilizer and, if necessary, (E) a polymerization inhibitor.