JPS6324537B2 - - Google Patents

Description

Detailed Description of the Invention The present invention is characterized by cigarette flame resistance, that is, when a lit cigarette is placed on the sheet surface and stepped on, the sheet surface is not likely to be destroyed by heat or cigarette ash will adhere to it. The present invention relates to a method of manufacturing an interior material having an excellent and sharp uneven pattern.

BACKGROUND ART In recent years, interior materials for building materials having an uneven pattern have been widely used as flooring materials and wall materials because of their good fashionability. However, the surface of conventional flooring materials with uneven patterns is coated with a thermoplastic resin composition, particularly a soft polyvinyl chloride (hereinafter abbreviated as PVC) composition, and has the disadvantage of poor resistance to heat, especially cigarette flames. There is.

The present applicant has already proposed a method for manufacturing a coated uneven interior material with excellent cigarette flame resistance in JP-A-54-120657. This is published in Japanese Unexamined Patent Publication No. 1973
120657 contains at least one member selected from PVC, a reactive plasticizer, a photosensitizer, a tin stabilizer, a phosphite, and a non-coloring antioxidant, and optionally (E) a polymerization inhibitor. The invention relates to coating an uneven patterned surface with a PVC composition obtained by heat-molding a composition and then reacting it by irradiation with active energy rays.

However, the patent states that the surface to be laminated already has an uneven pattern, which makes lamination more difficult than in the case of a flat surface, and that it is difficult to laminate a PVC composition that has already been cured by reaction with active energy rays. It is difficult to laminate because it does not soften easily during heat fusion, and since the PVC composition is laminated on top of a foam with an uneven pattern, the foam may deform during actual lamination or there may be differences in the sharpness of the unevenness. It has the disadvantage of lacking in

The present inventors investigated methods to improve this drawback, and found that
The PVC sheet is first laminated to a foam layer that can be chemically embossed, then heated and foamed to cover it.
After forming the PVC textured foam, the top-coated uncrosslinked active energy ray-curable PVC sheet is crosslinked by irradiation with active energy rays to create an interior material with excellent cigarette flame resistance and a sharp textured pattern. We discovered a manufacturing method and completed the present invention.

Crosslinkable by the active energy rays of the present invention
The PVC used in the PVC composition (hereinafter referred to as PVC composition A) and the PVC composition containing a foaming agent that can form an uneven pattern by heating (hereinafter referred to as PVC composition B) have an average degree of polymerization of 700 to 700. 4000 homopolymers of vinyl chloride or monomers copolymerizable with vinyl chloride, such as vinyl acetate, acrylonitrile,
It consists of a copolymer of one or more of styrene, (meth)acrylic acid ester, ethylene, propylene, butylene, etc., alone or in a mixture.

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 elastomers that can impart flexibility to the composition are preferred. Examples of such elastomers include natural rubber, nitrile rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, synthetic rubber such as acrylic rubber, chlorinated polyethylene, ethylene-vinyl acetate copolymer, and ethylene-vinyl acetate-vinyl chloride. Examples include graft copolymers.
When this elastomer is blended with PVC,
The amount is usually 1 to 30 parts, preferably 3 to 10 parts, per 100 parts by weight of PVC.

The PVC composition A of the present invention typically contains a reactive plasticizer,
Contains a photosensitizer. Such reactive plasticizers are those normally used for PVC,
It has at least two polymerizable unsaturated bonds and has good compatibility with PVC. Specifically, aliphatic polyhydric alcohols such as ethylene glycol, butylene glycol, 1,6-hexanediol, propylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, glycerin, and acrylic acid or Polyfunctional acrylic monomers obtained from methacrylic acid, aliphatic unsaturated allyl esters such as diallyl maleate and diallylitaconate, bisphenol type epoxy resins, polyvalent epoxy compounds such as epoxidized soybean oil, and acrylic acid, methacrylic acid. Epoxy acrylates obtained from unsaturated acids such as acids, unsaturated polyesters, dibasic acids such as phthalic anhydride, terephthalic acid, adipic acid, glycols such as ethylene glycol, propylene glycol, butylene glycol, and acrylic acid, methacrylic acid, etc. and unsaturated monobasic acids, such as bismethacryloyloxyethylene phthalate. Particularly preferred reactive plasticizers are those having at least one aromatic ring.

In addition, photosensitizers facilitate the crosslinking reaction of reactive plasticizers caused by photoexcitation upon irradiation with active energy rays, such as benzoyl, α-methylbenzoyl, α-allyl benzoyl, benzoin methyl ether, benzoin isopropyl. Ether, benzoin-sec-butyl ether, acetophenone, benzophenone, P-bromobenzophenone, 4,4'-tetramethyldiaminobenzophenone, diphenyl disulfide, tetraethylthiural disulfide, decylallyl sulfide, decyl Examples include thiobenzoate, benzyl acetyl, uranyl nitrate, eosin or thionine. Other aromatic nitro compounds such as trinitroaniline, nitronaphthalene, 5-nitroacenaphthene, 2-nitrofluorene, picramide, quinones such as naphthoquinone, anthraquinone, 2,3-diphenylanthraquinone, anthrone, pyrylium salts It is preferable to use the above-mentioned photosensitizers in combination with the above-mentioned photosensitizers to be more effective. Among these, benzoin compounds are preferred, and benzoin isopropyl ether is particularly preferred.

Incidentally, a stabilizer or an antioxidant can be added to the PVC composition A of the present invention.

Such stabilizers are normally those used in PVC, such as lead salts such as white lead, tribasic lead sulfate, tribasic lead maleate, and silicates; lead, cadmium, barium, and zinc. , metal soaps containing calcium, etc., and stearic acid, lauric acid, ricinoleic acid, naphthenic acid, etc.; tin-based stabilizers, phosphite esters, etc., which will be described later. Particularly preferred are tin stabilizers and phosphite esters.

The tin stabilizer mentioned above has the general formula R′pSnY ₄
-p (wherein R' is alkyl having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, heptyl, hexyl, pentyl, octyl, Y is lauric acid,
Maleic acid is a monovalent residue of a mercaptan compound. Further, p is an integer of 1 to 3. ). 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 dioctyl. Laurates such as malate, malate series, methyltin sulfide, n-butyltin sulfide, n-octyltin sulfide, methyltin tris (n-octylthioglycolate), n-
Butyltin tris (isooctylthioglycolate), n-butyltin tris (3,4,5-trimethylthiomalate), n-octyltin tris (cyclohexyl-3-mercaptopropionate), ethyltin tris (ethyl-2 -Mercaptomyristate), isopropyltin tris(methoxyethyl-3-mercaptopropionate),
n-propyltin tris(methyl-2-mercaptobenzoate), methyltin trisoctyl mercaptide, isoamyltin tris(tetrahydrofurfuryl-3-mercaptopropionate), mono-n-butyltin monoisooctylthioglycolate sulfate Sulfur-containing organotin stabilizers such as ido, mono-n-octyltin monocyclohexylthioglycolate sulfide, dimethyltinbis(isooctylthioglycolate), and di-n-octyltinbis(isooctylthioglycolate). can be mentioned. In particular, mercaptide-based tin stabilizers such as dimethyltinbis(isooctylthioglycolate) and dibutyltinbis(isooctylthioglycolate) are most effective in preventing coloration during heating. Other metal soaps, lead-based stabilizers, etc. 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. tris (nonylphenyl) phosphite, trisooctyl phosphite, trilauryl phosphite,
Examples include triisodecyl phosphite, triotadecyl phosphite, trilauryl trithiophosphite, trischloroethyl phosphite, dibutylhydrodiene phosphite, and the like.

In addition, non-coloring antioxidants are usually colorless antioxidants that are used and do not color PVC compositions. -(t-amyl)hydroquinone, 2,5-di-(t-butyl)
Hydroquinone, hydroquinone series such as 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-
Monophenols such as 4-n-butylphenol, 4,4'-dihydroxyphenyl, 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-
Bis-, tris-, polyphenols such as (2-methyl-4-hydroxy-5-t-butylphenyl) butane, thio such as 4,4'-thiobis-(6-t-butyl-4-methylphenol), etc. N as a bisphenol type, non-coloring amine type antioxidant,
N'-di-0-tolylethylenediamine, N,
N'-di-2-naphthyl-P-phenylenediamine, others include dilaurylthiodipropionate, distearylthiodipropionate, distearyl-β,β'-thiodibutyrate, 2-mercaptobenzimidazole, (nonylphenyl) phosphite, tris(mono- and di-nonylphenyl) phosphite, alkylaryl phosphite, and the like.

The above-mentioned tin-based stabilizers, phosphite esters, and non-coloring antioxidants can be used alone or in combination, but the tin-based stabilizers are most preferably used.

In addition to the above-mentioned components, a polymerization inhibitor may be added to the PVC composition A of the present invention, 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 PVC composition A of the present invention if necessary. However, non-reactive plasticizers such as dioctyl phthalate, dibutyl phthalate, dibutyl lauryl phthalate, dihebutyl phthalate, etc. may be used in an amount that can impart flexibility to the composition, and specifically, the amount is sufficient to impart flexibility to the composition. Te1~
Used in an amount of 30 parts.

The amount of the above-mentioned reactive plasticizer in the PVC composition A of the present invention may be any amount as long as it facilitates the foaming of the PVC composition B;
100% modulus is 4Kg/ ^mm2 or less, preferably 3
The amount is such that it is less than Kg/mm ² , and specifically,
It is 20 parts or more for 100 parts of PVC, considering that the final interior material will not be too rigid.
20 to 50 copies is appropriate.

The content of photosensitizer in the PVC composition A of the invention is related to the amount of reactive plasticizer and is usually from 0.001 to 10% by weight, based on the weight of reactive plasticizer. 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 the tin-based stabilizer, phosphite ester and non-coloring antioxidant in the PVC composition A of the present invention is usually 0.05 to 5 parts, preferably 0.5 to 2 parts, based on 100 parts of PVC. . Even when two or more of these three types of compounds are used, they are used in the above amounts. 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 not preferred. If PVC composition A is highly sticky, add a known lubricant such as higher alcohol, stearic acid, glycerin monostearate, ethylene bisstearamide, polyethylene glycol, liquid paraffin, polyethylene wax, etc. to 100 parts of PVC. If 0.1 to 1 part is added to the water, the tackiness can be reduced.

A polymerization inhibitor can be added to the PVC composition A of the present invention, but when adding such a polymerization inhibitor, the amount of the inhibitor is related to the amount of the reactive plasticizer, and usually the reactive plasticizer is It is used in an amount of not more than 5% by weight, preferably not more than 2% by weight, based on the weight of.

The composition containing the above-mentioned components is not a usual sol-type composition, but is heat-molded by calendering, extrusion molding, injection molding, or the like. The heating temperature at this time is usually 150 to 230°C.

Note that PVC composition A is usually heat-molded onto PVC composition B by the method described above, and then cured by irradiation with active energy rays. Active energy rays at this time include α rays, β rays, γ rays, ultraviolet rays, high frequency waves, etc., and especially 1800~
Actinic radiation having a wavelength of 7000 Å 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.

Examples of the blowing agent added to the PVC composition B used in the present invention include diazoaminobenzene,
1,3-diphenyltriazene, azodicarbonamide, 1,1'-azo-bisformamide, 2,
Azo compounds such as 2'-azo-isobutyronitrile and azohexahydrobenzonitrile; hydrazide compounds such as benzenesulfonyl hydrazide and P,P'-oxy-bis-benzenesulfonyl hydrazide; N,N'-dinitrosopentamethylene Examples include nitroso compounds such as tetramine.

In the present invention, PVC composition B is coated with PVC composition A and then heated to form an uneven pattern. The embossing (uneven pattern) method is not limited at all except for the ultraviolet irradiation method described in JP-A-51-83661, and any method can be used. A specific method is to print on a PVC sol containing a foaming agent with an ink containing a foaming inhibitor and then heat and foam it (Japanese Patent Publication No. 46-42637), or conversely, print with an ink containing a decomposition accelerator for the foaming agent and then heat and foam it. (Japanese Patent Publication No. 43-15713), a method in which the above-mentioned reactive plasticizer is placed in a PVC sol containing a foaming agent, the sol is printed with peroxide-containing ink, and then heated and foamed (Japanese Patent Publication No. 1973-15713). 67373, Japanese Patent Publication No. 52-36901), etc., but the method shown in Japanese Patent Publication No. 46-42637 is the most widely used and is particularly preferred in the present invention.

Foam suppressants used in the method shown in the above-mentioned Japanese Patent Publication No. 46-42637 include, for example, hydrochloric acid, maleic acid, sorbic acid, salicylic acid, benzoic acid, oxalic acid, succinic acid, mannitol, acetic anhydride, anthraniline, and p-nitroaniline. and moronic acid, but others shown in the patent can also be used.

Examples of decomposition accelerators for the blowing agent used in the method disclosed in Japanese Patent Publication No. 43-15713 include zinc compounds such as zinc oxide, zinc caprylate, zinc nitrate, and zinc fatty acid soap; cadmium caprylate, cadmium caproate, Cadmium compounds such as cadmium laurate, cadmium myristate, and cadmium fatty acid soap; lead compounds such as lead carbonate, lead phthalate, lead phosphite, and lead stearate; urea, borax, ethanolamine, kericol, benzenesulfone hydrazide, etc. , but others shown in that patent can also be used.

The heating temperature at which the PVC composition B is heated and foamed is usually a temperature at which the foaming agent decomposes, specifically about 150 to 220°C.

In the present invention, PVC composition B is typically coated onto a substrate. The base materials used in this case include asbestos; PVC with glass fiber; linen felt; cotton cloth; nonwoven fabric; PVC board; paper, wood, metal plate; natural rubber, synthetic rubber, ethylene-vinyl acetate copolymer, polyurethane, urea resin, Examples include sheets and plates made of organic polymeric substances such as phenolic resins.

Next, one embodiment of the manufacturing method of the present invention will be described. 0.3
~2.0mm thick base material is coated with a foaming agent-containing undercoat layer,
For example, a PVC sol containing a foaming agent is coated to a thickness of 0.2 to 3 mm and semi-gelled at 120°C, and then a printed pattern made of ink containing a foaming inhibitor is printed to obtain the PVC composition B layer. The sheet of PVC composition A is then laminated to the PVC composition B layer. Next, foaming is performed at 200°C to obtain a textured foam. Furthermore, the PVC composition A layer is cured by irradiation with active energy rays to obtain an interior material having an uneven pattern with excellent cigarette fire resistance.

The resulting interior material has excellent surface hardness, transparency, abrasion resistance, and cigarette flame resistance. The reason why this interior material has such excellent effects is that the reactive plasticizer in PVC composition A 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. considered to be a thing.

The interior material obtained by the present invention is suitable for fashion floors, wall coverings, leather, etc. Note that it can also be used for other purposes.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 The following PVC composition A was heated in two rolls at 170°C for 10 minutes.
A sheet with a thickness of 0.3 mm was obtained by kneading for a minute.

On the other hand, the following PVC composition B was fused onto an asbestos board to a thickness of 0.3 mm, and printed thereon with the following ink containing a foaming inhibitor to obtain a processed board.

Next, a sheet made of the above-mentioned PVC composition A was heat-sealed onto the processed plate at 150° C. for 3 minutes.
This was heated and foamed in an oven at 200°C for 2.5 minutes to obtain a molded plate having an uneven pattern. Furthermore, using a high-pressure mercury lamp manufactured by Iwasaki Electric Co., Ltd., irradiation was performed once under the conditions of two 80 W/cm UV lamps, a distance of 15 cm from the light source, and a belt speed of 5 m/min to obtain an interior material having an uneven pattern. The interior material had excellent cigarette flame resistance and had a sharp uneven pattern, and the depth of the embossing was 1.7 mm.

Γ Compound PVC of PVC composition A (=1050) 100 parts DOP - trimethylolpropane trimethacrylate
40 Benzoin ethyl ether 0.4 Hydroquinone 0.05 Dimethyltin bisisooctyl thioglycolate 1.5 Trinonyl phenyl phosphorite 1.0 Γ Compounded PVC of PVC composition B 100 parts DOP 50 Azodicarbonamide 3 Titanium dioxide 5 Zinc white 1.5 Charcoal 10 2 Basic lead phosphite 2 Γ Formulation of ink with anti-foaming agent Vinyl chloride-vinyl acetate copolymer 10 parts Methyl ethyl ketone 55 Titanium oxide (55%) 22 Trimellitic anhydride 13 Example 2 Two bottles of PVC composition A of Example 1 using a roll
The mixture was kneaded at 170°C for 10 minutes to obtain a sheet with a thickness of 0.15 mm. In addition, two rolls of the following PVC composition C are 170
The mixture was kneaded at ℃ for 10 minutes to obtain a sheet with a thickness of 0.15 mm. Next, laminate both sheets with a laminating roll.
It was made into a 0.3mm thick sheet.

Hereinafter, an interior material having an uneven pattern was prepared in the same manner as in Example 1 except that the 0.3 mm thick sheet obtained above was used instead of the 0.3 mm thick sheet obtained from PVC composition A in Example 1. Obtained.

The obtained interior material has good cigarette flame resistance,
It had a sharp uneven pattern and the depth of the embossing was 1.9 mm.

Γ Compound PVC of PVC composition C (=1050) 100 parts DOP 40 Trimethylolpropane trimethacrylate
- Benzoin ethyl ether - Hydroquinone - Dimethyltin bisisooctylthioglycolate 1.5 Trinonyl phenyl phosphorite 1.0 Comparative example 1 A sheet of PVC composition A obtained in Example 1 was irradiated with ultraviolet rays under the same conditions as Example 1. . The obtained cured sheet was used in the same manner as in Example 1 below. However, the ultraviolet irradiation step was omitted. The obtained interior material had good cigarette flame resistance, but the sharpness of the unevenness was inferior to that of the examples. The depth of the embossing was 1.2 mm.

Comparative Example 2 Asbestos board used in Example 1
A processed plate coated with PVC composition B and then printed was heated and foamed in advance at 200° C. for 2.5 minutes, but in the same manner as in Example 1 except that an interior material having an uneven pattern was obtained. Although the obtained interior material had good cigarette flame resistance, the sharpness of the unevenness was inferior to that of the examples.
The depth of the embossing was 0.9 mm.

Comparative Example 3 In Example 1, ultraviolet irradiation was performed first,
Thereafter, heating and foaming was performed to obtain an interior material having an uneven pattern. The obtained interior material had good cigarette flame resistance, but the sharpness of the unevenness was inferior to that of the examples. The depth of the embossing was 0.9 mm.

Comparative Example 4 The sheet of PVC composition A obtained in Example 1 was irradiated with ultraviolet rays in advance. Next, the asbestos board used in Example 1 was coated with PVC composition B,
Thereafter, the printed processed plate was heat-foamed at 200° C. for 2.5 minutes, and the above ultraviolet irradiation sheet was heat-fused at 150° C. for 4 minutes. The obtained interior material had good cigarette flame resistance, but the sharpness of the unevenness was inferior to that of the example. The depth of the embossing was 0.6 mm.

Comparative Example 5 An interior material was obtained in Example 1 without UV irradiation. The resulting interior material has an embossing depth of 1.7
Although it had unevenness of mm, its resistance to cigarette flame was extremely poor.

Claims (1)

[Claims] 1. (A) A polyvinyl chloride composition that can be crosslinked by active energy rays as a surface layer is coated on (B) a polyvinyl chloride composition layer containing a foaming agent that can be heated to form an uneven pattern, and then heated to form an uneven pattern. A method for producing an interior material having an uneven pattern, which comprises forming a pattern and then irradiating the surface layer with active energy rays to crosslink the surface layer.