JPH0686102B2 - Foamed decorative material and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a foam decorative material used for floor materials, wall materials and the like, and a method for producing the same.

[Prior art]

Conventionally, the following are known foamed decorative materials having a foamed resin pattern and methods for producing the same.

1) A method in which a foaming resin pattern is directly printed on a foamed raw fabric or a chemically embossed foamed raw fabric by screen printing or the like to heat and foam.

2) A method of forming a concavo-convex pattern on an original foam sheet by embossing.

3) A method of forming a foamed resin pattern using only chemical embossing.

However, in the method 1), the foamed resin pattern and the foamed resin layer are melted and coalesced with each other or part of them settles during heat-foaming, so that unevenness of steps, sharpness of edge portions, etc. are reduced. There was a flaw.

In the method of 2), the uneven edge portion becomes sharp,
It is difficult to synchronize the uneven pattern formed by embossing with the pattern such as printing formed on the foamed raw fabric.
Since the unevenness is formed on the back surface of the base material and it is not smooth, wallpaper,
There was a drawback that the workability as a floor material was poor.

In the method 3), the foaming inhibitor is unstable because it absorbs moisture from the atmosphere, and the ink containing the foaming inhibitor changes with time after adjustment, so that it is difficult to keep the foaming inhibiting effect constant. Therefore, the design of the surface formed by chemical embossing changes, and it is difficult to stably produce a multi-stage foamed pattern. Further, there is a drawback that it is difficult to express a sharp edge portion.

[Means for Solving the Problems]

The present invention has been obtained as a result of studies in view of the above circumstances.

That is, the present invention provides a transparent separation layer on the foamed resin layer,
By forming the foamed resin pattern thereon, it is possible to prevent the foamed resin pattern from sinking into the foamed resin layer and form a sharp foamed resin pattern.

The foam decorative material of the present invention comprises a foamed resin layer (1
2) is formed, and the substrate (1) is formed on the foamed resin layer (12).
It has a transparent resin layer (3) made of a resin having a softening point higher than that of the resin forming the foamed resin layer (12) and the foamed pattern (14), and the foamed pattern is further formed on the transparent resin layer (3). (14).

The most important feature of the present invention is the foamed resin layer (12).
A transparent resin layer (3) made of a resin having a softening point higher than that of the resin forming the foamed resin layer (2) and the foamed pattern (14) is provided at the boundary between the foamed pattern (14) and the foamed pattern (14). This transparent resin layer (3) has a foamed resin layer (12) and a foamed pattern (1
4) Preventing contact with the above, preventing mutual fusion during heating and foaming, and preventing sinking of foamed pattern in the foamed resin layer (12). As a result, the foamed pattern (14) on the transparent resin layer (3) becomes sharp.

Thus, the transparent resin layer (3) has a function of keeping the foamed pattern (14) formed on the transparent resin layer sharp. Therefore, even if the foamed pattern (14) is formed unevenly by using the foaming inhibitor in the present invention, it is possible to form a pattern having a significantly superior sharpness as compared with the conventional foamed pattern formed only by chemical embossing. it can.

Further, the foamed resin layer (12) is made uneven so that different design effects can be obtained. The unevenness can be formed by partially suppressing foaming of the foamed resin layer (12) or by partially providing a foamed portion.

The foam decorative material of the present invention can be provided with patterns (5, 6) formed of ordinary ink or the like in synchronization with the foam pattern to further improve the design effect.

This pattern can be provided on one or more surfaces of the foamed resin layer (12), the transparent resin layer (3), and the foamed pattern (14), and the design effect can be subtly changed by the combination thereof. it can.

It is also possible to form this pattern with an ink containing a foaming agent or a foaming inhibitor.

Next, the materials constituting the foam decorative material of the present invention will be described.

As the base material (1), a single material such as paper, cloth, non-woven fabric, asbestos, plastic sheet, metal plate such as iron and aluminum, or a composite material thereof can be used. In general, paper that is made flame-retardant or that is made incombustible by mixing paper with glass is used.

A thermoplastic resin can be used for the foamed resin layer (12). For example, polyolefins such as polyethylene and polypropylene: polyolefin-based copolymers such as ethylene-vinyl alcohol copolymers, polystyrene, polyphenylene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyamides such as nylon, polyurethane, poly A synthetic resin such as acryl such as methyl methacrylate is used, and as the foaming agent, a softening agent for the synthetic resin to be used is selected from the same foaming agents as those used for the heat-foaming ink constituting the foaming pattern (4) described later. Point, foaming temperature, or selected in consideration of the combination with the foaming inhibitor used in the composition that constitutes the foaming suppression pattern, and further added for the purpose of preventing thermal deterioration of the plasticizer and resin, controlling the foaming structure, etc. A stabilizer, a coloring agent, a foaming accelerator, a lubricant, a flame retardant, a filler and the like are appropriately kneaded to form a composition.

It is desirable that the resin constituting the foamed resin layer be gelled by heating, and a plastisol or organosol system is generally suitable in terms of coating suitability and the like.

The most commonly used thermoplastic resin is polyvinyl chloride, which has an average degree of polymerization of 700-2000 and a particle size of 0.2-
It is preferably 2 μm polyvinyl chloride. Normal,
40 to 80 parts by weight of dioctyl phthalate, dibutyl phthalate, tricresyl phosphite, chlorinated paraffin, etc. are added as plasticizers to 100 parts by weight of polyvinyl chloride. As the stabilizer, known compounds mainly containing lead, tin, zinc, cadmium, barium, etc., epoxidized oil and fat, and various chelators are used.

The foamed pattern (14) is often composed of the same raw material as that of the foamed resin layer (12), but an extender pigment or the like may be added to further impart printability. Further, in order to enable drying and gelation in a short time, it is often performed in an organo system using a solvent.

More specifically, the foamed pattern (14) is formed by using a heat-foamable ink obtained by mixing a foaming agent into ink using an appropriate vehicle, and the vehicle is ethyl cellulose, ethyl hydroxyethyl cellulose, Cellulose acetate brobionate, cellulose derivatives such as cellulose acetate, polystyrene resin, styrene copolymer resin, homopolymer or copolymer resin of acrylic or methacrylic resin, rosin ester resin, polyvinyl acetate resin, chroman resin, vinyltoluene resin, vinyl chloride. /
Using one or more of vinyl acetate copolymer resin, vinyl chloride resin, polyester resin, polyurethane resin, etc.,
Plasticizers, stabilizers, dispersants, extender pigments, colorants, solvents and diluents are appropriately added to these vehicles, and further inorganic agents such as sodium bicarbonate, ammonium carbonate, sodium boron hydride, and silicon oxyhydride as a foaming agent. Blowing agents, azodicarbonamide, azobisisobutyronitrile, dinitrosopentamethylenetetramine, paratoluenesulfonylhydrazide, azo series such as 4,4′-oxybisbenzenesulfonylhydrazide, sulfonylhydrazide series, N-nitroso 1-10, preferably 2-8, based on 100 parts by weight of the vehicle.
Parts by weight, and if necessary, a plasticizer, stabilizer,
A colorant, a foaming accelerator, a filler and the like are kneaded to prepare a heat-foamable ink, and the foamable pattern made of this heat-foamable ink is heat-foamed to form a foamed pattern (14). It is also possible to use, as the heat-foamable ink, one having the same composition as the foamed resin layer.

The transparent resin layer (3) may be a resin having a softening point higher than that of the resin forming the foamed resin layer (12) and the foamed pattern (14). The resin as the transparent resin layer (3) can be formed by laminating a film-shaped resin or by coating an ink-shaped or sol-shaped resin. For example,
Inks made of polyurethane, polyester, epoxy resin, etc. crosslinked with isocyanate, amine, etc., crosslinked polyvinyl chloride, high molecular weight polyvinyl chloride, ionizing radiation curable resin, etc. are coated and dried, and if necessary. Cured by heat, ionizing radiation, etc. or crosslinked, or crosslinked polyvinyl chloride, high molecular weight polyvinyl chloride,
A film of polyethylene terephthalate, polyethylene isophthalate / terephthalate copolymer, carbonate, polyimide, polyarylate, polyether ether ketone or the like is laminated with a known appropriate adhesive such as two-component curing type urethane or polyester adhesive. Is also good.

The thickness of the transparent resin layer (3) is preferably thick from the viewpoint of the effect of preventing the fusion of the foamed pattern (14) and the foamed resin layer (12), and is thin from the viewpoint of the drying property by the coating method and the price. Good, usually 1
˜50 μm, preferably 1˜20 μm.

Next, the ionizing radiation curable resin will be described.

Here, ionizing radiation refers to electromagnetic waves or charged particle beams having an energy quantum capable of crosslinking and polymerizing molecules, and there are various types, but industrially usable ones are ultraviolet rays or electron beams. In addition to this, gamma rays can also be used.

Examples of the ionizing radiation curable resin include prepolymers or oligomers having an ethylenically unsaturated bond in the molecule, such as unsaturated polyesters, polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate. Various acrylates, polyester methacrylate, polyether methacrylate,
One or more kinds of various methacrylates such as polyol methacrylate and melamine methacrylate, and a monomer having an ethylenically unsaturated bond in the molecule,
For example, styrene-based monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, and phenyl acrylate. Acrylic esters, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate, and other methacrylate esters, acrylamide, methacrylamide, and other unsaturated carboxylic acid amides, acrylic Acid-
2- (N, N-diethylamino) ethyl, methacrylic acid-
2- (N, N-dimethylamino) ethyl, acrylic acid-2
-(N, N-dibenzylamino) ethyl, (N, N-dimethylamino) methyl methacrylate, acrylic acid-2-
Substituted amino alcohol esters of unsaturated acids such as (N, N-diethylamino) propyl, ethylene glycol diacrylate, propylene glycol diacrylate,
Polyfunctional compounds such as neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol acrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, And / or a polythiol compound having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol, etc. It is formed by. The coating composition is obtained by optionally mixing the above compounds. In order to impart ordinary coating suitability to the composition, 5% by weight or more of the prepolymer or oligomer, and It is preferable that the amount of the monomer and / or polythiol is 95% by weight or less. Also, the flexibility of the coating film
A non-crosslinking thermoplastic resin, for example, a resin such as cellulose, urethane, butyral, or acrylic resin may be added in order to obtain the adhesiveness with the foamed resin layer (12).

As described above, the foamed pattern (14) and / or the foamed resin layer (12) formed on the transparent resin layer (3) can be made uneven by utilizing the effect of the foaming inhibitor. At this time, it can be applied in the form of an ink containing a foaming inhibitor.

Compounds that prevent the decomposition of the foaming agent or the function of the foaming accelerator that promotes foaming of the foaming agent, that is, as the foaming inhibitor, maleic acid, fumaric acid, adipic acid, 1,
Organic acids such as 2-phthalic acid, especially organic acids containing at least two carboxyl groups and one hydroxyl group and having 2 to 12 carbon atoms: organic acid halides having 2 to 20 carbon atoms, especially acid chlorides: C2-C20 organic acid anhydride: C2-C20 polyvalent aromatic alcohol and ketone having two functional groups: C3-C12 saturated amine or unsaturated 6-10 membered ring A compound having an effect of increasing the foaming temperature is selected from amines and the like depending on the application, for example, by combining with a foaming agent, a foaming auxiliary agent, and a stabilizer used for a heat-foamable material. A foam suppressing pattern is printed using a foam suppressing ink obtained by kneading by appropriately adding a colorant, a plasticizer, a stabilizer and the like, and the foam suppressing pattern part is suppressed from heat foaming.

Regular patterns (5) and (6) mean patterns composed of an ink composition containing no foaming agent or foaming inhibitor.

Next, the method for producing the foamed decorative material of the present invention will be described. First, on the surface of the substrate (1) (A), a foamable resin layer (2) made of a resin composition containing a thermal decomposition type foaming agent is provided. Step (B) A resin having a higher softening point on the surface of the expandable resin layer (2) than the resin forming the expandable resin layer (2) and the expandable pattern (4) on the surface of the substrate (1) Step (C) of providing a transparent resin layer (3) made of (D) Foaming step (D) of providing a foamable pattern (4) made of a resin composition containing a thermal decomposition type foaming agent on the surface of the transparent resin layer (3) It consists of heating the whole above a temperature.

The structure of the decorative material before heat foaming is shown in FIG. The structure of the decorative material after the heat-foaming treatment is shown in Figs. The layers and patterns in the steps (A), (B), and (C) described above are formed by coating or printing, but the gravure method is generally used as the printing method, but offset, letterpress, silk screen, etc. are also known. The following printing methods can be used.

Further, in the step (B), the transparent resin layer (3) formed on the film may be attached by a dry laminating method using an adhesive.

The ink that forms the normal pattern is the surface of the transparent resin layer (3),
It can be printed on one or more of the back and the surface of the foamable pattern (4).

It goes without saying that the printing color can be multicolored for both the foaming pattern (4) and the normal patterns (5) and (6).

After the foamable resin layer (2) is provided, the transparent resin layer (3) is provided, and after the foamable pattern (4) is provided, drying is performed at a foaming temperature or lower, and coating or printing work in each subsequent step is performed. And the heat foaming step can be advantageously performed.
Further, by making the drying temperature after providing the foamable pattern (4) higher than the foaming temperature of the foamable resin layer (2) and the foamable pattern (4), drying and foaming can be performed simultaneously. It can be omitted.

In the foamed decorative material having the structure shown in FIG. 2, a regular pattern (5), a transparent resin layer (3) and a foamable pattern (4) are sequentially provided on the foamable resin layer (2), and then foamed by heating. It is manufactured by The structure shown in FIG. 3 or 4 has a foamable resin layer (4) and a regular pattern (6) on the transparent resin layer (3).
It can be manufactured appropriately by changing the order of providing. Fourth
The structure shown in the figure can be manufactured by sequentially providing a regular pattern (5), a transparent resin layer (3), a regular pattern (6) and a foamable pattern (4).

[Example-1] The base material (1), the expandable resin layer (12), and the base material (1) shown in FIG.
The foam decorative material in which the normal pattern (5), the transparent resin layer (3) and the foam pattern (14) are sequentially provided will be described.

The substrate WK-70 NRD was used. (Made by Kojinsha) Knead with the above mixture and adjust the viscosity with mineral spirits.
Adjust to 3000 cps and coat the substrate with a thickness of 160 μm. Then, it was heated at 160 ° C. for 70 seconds to carry out dry gelation.

Normal pattern Normal ink NWP (manufactured by Showa Ink Kogyo Co., Ltd.) was provided on the foamable resin layer by a gravure printing method.

Transparent resin layer Two-component curing type urethane-based ink UM No.15 (made by Morohoshi Ink Co., Ltd.) is printed by gravure printing to a thickness of 2 μm.

Foaming pattern The pattern of the foaming ink NSFT No. 8 (manufactured by Showa Ink Kogyo Co., Ltd.) was provided by synchronizing with the normal pattern by the gravure printing method. The foamable pattern was printed using a plate having a plate depth of 100 μm.

Foaming ink needs to be gelled after printing, 140 ℃
And dried for 15 seconds.

Foaming Foaming was performed by heating at 210 ° C for 50 seconds to obtain a foamed decorative material.

In the produced foam decorative material, a sharp foam resin pattern was formed on the edge portion of the uneven portion in synchronization with the printing.

[Example-2] In Example-1, a transparent resin layer was formed into a polycarbonate film having a thickness of 50 µm by using a polyurethane adhesive (main ingredient Takelac A515 and curing agent Takenate A in a weight ratio of 10).
(Blended at 0: 5) to form a dry laminate.

For the foaming of the foamable pattern, immediately after printing the foaming ink, heating was performed at 210 ° C. for 60 seconds to dry the solvent, gelate, and foam all at the same time. (Others are the same as in Example-1) The foamed decorative material produced had a sharp foamed resin pattern in synchronism with printing.

〔The invention's effect〕

A sharp foam pattern on the edge of the uneven portion can be formed in synchronization with printing. Further, as compared with the case where the foamed ink is directly printed on the foamed resin layer, the foaming pattern at the time of foaming does not settle or coalesce into the foamed resin layer.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a decorative material before heat foaming in the production of the foamed decorative material of the present invention. 2, 3, 4, and 5 are schematic sectional views of the foam decorative material of the present invention. 1 ... Substrate 2 ... Foaming resin layer 3 ... Transparent resin layer 4 ... Foaming pattern 5,6 ... Normal pattern 12 ... Foaming resin layer 14 ... Foaming pattern

Claims (10)

[Claims] 1. A foamed resin layer (12) is formed on a substrate (1), and a foamed resin layer (12) and a foamed pattern (14) on the substrate (1) are formed on the foamed resin layer (12). A transparent resin layer (3) made of a resin having a softening point higher than that of the constituent resin,
Furthermore, a foam decorative material having a foam pattern (14) on the transparent resin layer (3). 2. The transparent resin layer (3) having a regular pattern (6), and the transparent resin layer (3) and / or the regular pattern (6) having a foamed pattern (14). The foamed decorative material according to 1). 3. A transparent resin layer (3) having a foamed pattern (14), and further, the transparent resin layer (3) and / or the foamed pattern (1).
4) The foam decorative material according to claim 1, which has a regular pattern (6) on the top. 4. The foamed decorative material according to claim 1, which has a normal pattern (6) on the foamed resin layer (12). 5. The foam decorative material according to any one of claims 1 to 4, wherein the normal pattern (6) is made of a resin composition containing or not containing a foaming inhibitor. 6. A step of providing a foamable resin layer (2) made of a resin composition containing a pyrolytic foaming agent on the surface of a substrate (1),
On the surface of the foamable resin layer (2), a transparent resin made of a resin having a softening point higher than that of the resin forming the foamable resin layer (2) and the foamable pattern (4) on the surface of the substrate (1). The step of providing the layer (3), the step of providing the foamable pattern (4) made of a resin composition containing a pyrolytic foaming agent on the surface of the transparent resin layer, and then the foamable resin layer ( 2) and a method for producing a foam decorative material, which comprises the step of foaming the foamable pattern (4). 7. A foamable resin layer (2), a foamable pattern (4),
The method for producing a foamed decorative material according to claim (6), which comprises a treatment of drying at a foaming temperature or lower in each step of providing the transparent resin layer (3). 8. The method according to claim 6, further comprising the step of providing a pattern made of a resin composition containing a thermal decomposition type foaming agent or a foaming inhibitor on the surface of the foamable resin layer (2). Method of manufacturing foamed decorative material. 9. A foamable resin layer (2), a transparent resin layer (3),
The method for producing a foam decorative material according to any one of claims (6), (7) and (8), which comprises a step of providing a normal pattern on one or more surfaces of the foamable pattern (4). 10. A method in which the drying temperature after providing the foamable pattern (4) is set higher than the foaming temperatures of the foamable resin layer (2) and the foamable pattern (4), and the foaming is performed simultaneously with the drying. Item 6. A method for producing a foam decorative material according to any one of items (6), (7), (8), and (9).