JP2890203B2 - Manufacturing method of foam decorative material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a foamed decorative material, and when used for interior decoration, can be easily and easily replaced without adjusting the base. The present invention relates to a method for producing a foamed decorative material.

[Prior art] In recent years, as interior decoration materials have become more highly directional, they gradually have three-dimensional high design, soft touch, rich volume, light weight and excellent workability. The use of highly foamed wall materials is increasing.

Conventionally, as a method for producing such a product having high foaming, a large amount of a foaming agent is added to a synthetic resin such as vinyl chloride in order to obtain a high foaming ratio on a base material such as flame-retardant paper. It is known that a foamed composition containing a large amount of a filler is laminated and heated and foamed to obtain a product in order to reduce flammability, dimensional stability during construction, and cost reduction of the product.

[Problems to be Solved by the Present Invention] At present, demand for replacement demand is increasing due to the image change, dirt or breakage of the interior decoration using the decorative material such as the wall material.

However, when the foaming wall material product manufactured by the conventional method is replaced, when the foaming layer is peeled off and the foamed layer is manufactured with a high expansion ratio, the foamed cell film thickness is extremely thin,
Moreover, since the filler is mixed in a large amount, the strength of the foamed layer is low, and the bonding strength between the foamed layer and the base material is strong.

Therefore, the cell structure of the foam layer is destroyed during the peeling work, and the residue of the foam layer partially adheres to the wall base. In this state, it is difficult to reconstruct a new wall material, and it is necessary to remove the adhered residue. Yes, a lot of man-hours for cleaning work,
It has the disadvantage of requiring labor and time.

The present invention has been made as a result of intensive studies to solve the above-mentioned conventional problems, and as a result, to provide a highly foamed decorative material which has a high bonding strength between a base material and a foamed layer, and can peel off the base material from a wall substrate. is there.

[Means for Solving the Problems] The present invention forms a smooth and uniform thin layer of a synthetic resin composition mixed with a foaming crosslinking agent or a foaming inhibitor on a base material, and then forms a foamable layer on the layer. A synthetic resin layer is laminated and then heated and foamed to infiltrate the foaming cross-linking agent or foaming inhibitor into the foamable synthetic resin layer, and the foamable synthetic resin layer is sequentially coarsened from the surface toward the substrate surface. The method of the present invention is a method for producing a foam decorative material, which comprises forming a foam having a dense and dense gradient structure formed from tiny bubbles into fine bubbles.

[Operation] Hereinafter, the present invention will be described in detail.

In the present invention, first, a synthetic resin composition mixed with a foaming crosslinking agent or a foaming inhibitor is smoothly laminated on a base material, and then heated and dried to form a uniform thin layer.

As the means, a coating method such as a rotary screen method, a gravure method, or a doctor method is particularly preferable, but other methods such as a calendering method or an extrusion method that enable lamination of a smooth and uniform thin layer are applied. May be.

Whichever method is used, the thickness of the thin layer is 0.01 to
It is formed to have a thickness of 0.05 mm. The reason for setting the thickness of the thin layer in this manner is that the foaming cross-linking agent or foaming inhibitor mixed in the layer is a thin layer that sufficiently satisfies the penetrating effect on the foamable synthetic resin layer in the process described below. It is an essential layer thickness, and by doing so, the foamable synthetic resin layer has a dense-dense gradient structure that gradually changes from its surface to the substrate surface from coarse cells to micro-bubbles. Since the dense structure is formed, the bonding strength between the base material and the synthetic resin foam layer becomes strong. Desirably 150g / 3 for bonding strength
0mm width or more. Below this strength, the bonding strength is not always sufficient and one of the foamed layers may remain.

The present invention is such a product as a wall covering material, by applying this, when peeled from the wall base,
The synthetic resin foam layer can be smoothly separated from the base material without causing delamination between the base material and the base material.

However, if the layer thickness is 0.01 mm or less, the layer thickness is too thin, and the penetration amount of the foaming crosslinking agent or foaming inhibitor into the synthetic resin foam layer is generally insufficient irrespective of the amount of the additive mixed. However, the infiltration effect is incomplete and a foam layer having a gradient of coarse and fine gradient cannot be obtained, so that the bonding strength between the substrate and the synthetic resin foam layer changes, and a desired product cannot be obtained.

Further, if the thickness of the layer is 0.05 mm or more, the penetration amount of both additives is excessively large, the foaming property of the synthetic resin foaming amount is inhibited and the foaming property is extremely small, and in some cases, the non-foaming foam layer having a very low density gradient is poor. In terms of the bonding strength to form
It is satisfactory enough, but it is not very soft, three-dimensional design and volume as foam decorative material. The weight regulation in the fireproof standard applied when used as an interior material cannot be cleared, and the product cost is undesirably high.

The base material used in the present invention is paper, flame-retardant paper, aluminum hydroxide paper, glass cloth, nonwoven fabric, etc., alone or in a laminate of two or more of these, all of which have very little elasticity. Use a substrate that is easy to peel off.

When a thin layer formed on a substrate is formed by a coating method, a paste-type paint or a solvent-type paint is applied to a synthetic resin composition mixed with a foaming crosslinking agent or a foaming inhibitor.

Examples of the synthetic resin used for the paste-type coating material include polyvinyl chloride, a copolymer of polyvinyl acetate, polyethylene, polyurethane, and the like, a homopolymer of vinyl chloride, and a mixture thereof, in addition to the vinyl chloride homopolymer.

Further, as the synthetic resin used for the solvent type paint, polyvinyl chloride, polyvinyl chloride and polyvinyl acetate copolymer or acrylic resin, polyurethane resin or polyester resin alone or using a copolymer or a mixture thereof, A general-purpose solvent such as methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, ethyl acetate, and toluene may be used as the solvent.

Examples of the foaming crosslinking agent of the present invention include dithiol-S-triazine derivatives (for example, S-triazine derivatives such as 2-dibutylamino, 2-dimethylamino and 2-octylamino) and metal salts thereof (for example, alkalis such as Li and Na). Metal salts, alkaline earth metal salts such as Ca and Mg) can be used, but 2-dibutylamino-2-triazine derivatives are particularly preferable.

Examples of the foam inhibitor include benzotriazole, organic acids (eg, maleic acid, fumaric acid, adipic acid), halogenated organic acids (eg, galephthaloyl chloride, tetrachlorophthalic anhydride, etc.), and organic acid anhydrides (eg, maleic anhydride). Acid, trimellitic anhydride, etc.), but it is particularly preferable to use benzotriazole or trimellitic anhydride.

The amount of the above-mentioned foaming crosslinking agent or foaming inhibitor added in the paint is, in the case of a solvent type paint, the resin solid content of the paint.
10 to 150 parts by weight, preferably 50 to 100 parts by weight per 100 parts by weight
Parts by weight, and in a paste type paint, 0.1 to 5.0 parts by weight, preferably 0.5 to 5.0 parts by weight, based on 100 parts by weight of the resin of the paint.
If the lower limit is 10 parts by weight or less than 0.1 part by weight, the permeability at the time of heating and foaming into the foamable synthetic resin layer is insufficient, and the foaming cross-linking effect or foaming suppressing effect is poor. In the foaming step, a foamed layer having a dense / dense gradient structure of the foamed layer cannot be obtained, so that the bonding strength between the base material and the synthetic resin foamed layer is reduced, causing a problem in the peelability with respect to the construction wall surface, and the upper limit of 150. Parts by weight and 5
If the amount is more than 100 parts by weight, the foaming crosslinking effect or the foaming suppressing effect acts excessively, so that the problem with respect to the peelable property can be solved. Further, it becomes hard and undesirably causes the above-mentioned various defects.

When the thin layer is formed by using a calendering method or an extrusion method, as the synthetic resin composition, in addition to the homopolymer of vinyl chloride, polyvinyl chloride and polyvinyl acetate copolymer or acrylic resin, polyurethane or polyester Either a resin alone or a copolymer or a mixture thereof can be used.

The present invention provides a foam crosslinking agent or foam inhibitor for the composition,
Materials such as a plasticizer, a stabilizer and a filler are appropriately selected and used according to the resin used.

After laminating and forming the thin layer on the base material, a foamable synthetic resin layer is laminated on the thin layer. As a method for forming the foamable synthetic resin, processing methods such as a calendering method, an extrusion method, and a coating method can be used, and a coating method is particularly preferable.

Colored or uncolored sheet under processing conditions below the decomposition temperature of the foaming agent contained in the foamable synthetic resin layer using any of the above methods, the sheet thickness is 0.10 to 0.30 mm, preferably 0.15 to 0.25 It is laminated so that it becomes mm.

This is because when the foamable layer is formed by heating the foamable synthetic resin, if the thickness is less than 0.10 mm, the layer thickness is too thin, so the foaming crosslinking agent or foaming inhibitor in the thin layer below is laminated thereon. Not only lacks softness, volume and three-dimensionality, but also has a coarse-dense gradient structure as described below. In addition, if it is 0.30 mm or more, it becomes too heavy in weight, causing a problem in workability as an interior material, and it is not preferable because it is expensive in terms of product cost.

As the synthetic resin used for the foamable synthetic resin layer, in addition to the vinyl chloride homopolymer, a copolymer of polyvinyl chloride and polyvinyl acetate, polyethylene, polyurethane, or the like, or a homopolymer of vinyl chloride and a mixture of these are used. Compounding agent, plasticizer according to the type of synthetic resin, etc.,
Stabilizers, lubricants, chelators, fillers, coloring agents and the like can be appropriately selected and combined and added.

Further, as a foaming agent used for the foamable synthetic resin layer,
A general-purpose, heat-decomposable blowing agent such as azodicarboxylic acid amide, PP'-oxybisbenzenesulfonyl hydrazide, azobisisobutyronitrile is added to 100 parts by weight of the resin.
To 10 parts by weight, preferably 4 to 7 parts by weight.
When the amount is less than 2 parts by weight, the amount is too small, so that when forming a foamed layer by heating, neither the foaming crosslinking effect nor the foaming inhibiting effect is insufficient, and a dense-dense gradient structure cannot be obtained.

Also, if the addition amount is 10 parts by weight or more, the expansion ratio is too high,
The surface roughness of the product is conspicuous, and the surface wear strength and the bonding strength with the base material are undesirably reduced.

When the foamable synthetic resin layer is foamed under heating conditions at or above the decomposition temperature of the foaming agent contained by using a heating furnace, the foaming crosslinking agent or foaming inhibitor in the thin layer below the foaming synthetic resin layer is contained in the foamable synthetic resin layer. And the amount of permeation increases on the substrate side, and gradually decreases as the distance increases.

As a result, the foaming state of the foamable synthetic resin layer is suppressed from foaming on the substrate side to form extremely small bubbles, and the influence of the foaming crosslinking agent or foaming inhibitor decreases gradually as the distance increases, and the bubbles are gradually increased. The bonding strength between the base material and the foamable synthetic resin layer obtained as a foamed synthetic resin layer having a coarse-dense gradient structure in which the foaming state of the foamable synthetic resin layer is gradually formed from small bubbles to coarse bubbles from the base material toward the surface. Is 150g / 30m
The width can be as large as m or more, and the residue of the expandable synthetic resin does not remain when peeled off from the wall base.

Therefore, when the interior decoration material such as wallpaper is replaced, a part of the foam layer does not remain, and the replacement operation is easy.

Incidentally, the decorative material obtained in the present invention is formed on the surface thereof by using a squeezing roll to form an uneven pattern, or a gravure printing method, a rotary screen method, a flexographic printing method, etc. By applying a printing pattern on the surface by using a squeezing roll on the surface, a product with a variety of three-dimensional and high design properties can be obtained.

[Embodiment] FIGS. 1 and 2 show an embodiment of the present invention, and the present invention will be described in detail with reference to these drawings. According to the present invention, as shown in FIG. 1, a thin layer 2 composed of a synthetic resin composition mixed with a foaming crosslinking agent or a foaming inhibitor is uniformly formed on a base material 1 and a foamable synthetic resin layer 3 is formed on the surface thereof. Are laminated.

When the laminate shown in FIG. 1 is heated in a heating furnace to a temperature equal to or higher than the decomposition temperature of the foaming agent in the foamable synthetic resin layer 3, the foaming crosslinking agent or foaming inhibitor in the thin layer 2 becomes foamable synthetic resin layer. 3
As the penetration amount increases toward the base material 1 side and goes away, that is, the penetration amount gradually decreases toward the surface side of the foamable synthetic resin layer 3, the penetration amount increases as shown in FIG. Is gradually restricted from the surface of the base material toward the surface of the foamable synthetic resin layer 3, so that the foam cells are formed as a foam having a close-packed gradient structure from the base material toward the surface. Although FIG. 2 shows the surface with the concavo-convex pattern 4 and the print pattern 5 applied thereto, it is possible to obtain a product with a more three-dimensional appearance and high design by applying the concavo-convex pattern and the print pattern. Can be.

Example 1 A paste made of a polyvinyl chloride resin composition of the following formulation A containing a base material of fire-retardant paper for backing wallpaper (manufactured by Sanyo Kokusaku Pulp Co., Ltd., trade name: 70AF-10) and containing a foaming crosslinking agent on the base material. Paint the paint with a rotary screen printing machine to a thickness of approximately
After the entire surface is coated smoothly to a thickness of 03 mm, it is heated at a temperature of about 150 ° C. for about 1 minute using a hot-air drying furnace, and gelled and dried to form a thin layer.

Next, a paste paint comprising a polyvinyl chloride resin composition of the following formulation B containing a foaming agent was uniformly applied on the layer using a comma coater so as to have a thickness of about 0.20 mm. The resin composition was heated at a temperature of about 160 ° C. or lower for about 1 minute below the decomposition temperature of the foaming agent using a drying oven, and the resin composition was gelled and dried to form a vinyl chloride foamable synthetic resin layer. The foaming crosslinking agent in the thin layer is allowed to penetrate into the polyvinyl chloride resin foaming layer.

Formulation A: Polyvinyl chloride resin (= 1200) (resin for paste) 100 parts by weight DOP 55 parts by weight Ba-ZN stabilizer 3 parts by weight Triazinethiol DB (foaming crosslinking agent) 5 parts by weight Filler 20 parts by weight Formulation B : Polyvinyl chloride resin (= 800) (resin for paste) 100 parts by weight DOP 65 parts by weight Na-Zn stabilizer 3 parts by weight Azodicarboxylic acid amide (foaming agent) 6 parts by weight Filler 80 parts by weight Titanium white pigment 10 5 parts by weight of a diluent 5 parts by weight Next, when the laminate is heated at a temperature of about 210 ° C. for about 1.5 minutes using a heating foaming furnace, the foaming agent in the composition B is decomposed and foamed, and The foaming crosslinking agent in Formulation A that has permeated the vinyl synthetic resin layer causes a crosslinking reaction with the synthetic resin component.

At this time, since the foaming cross-linking agent that has permeated into the formulation B has a large amount of permeated surface on the substrate side and decreases gradually toward the surface, the cross-linking reaction becomes dense on the substrate side and becomes coarser toward the surface. As a result, as for the foaming of the synthetic resin layer of Formulation B, a foam cell is obtained as a foam having a coarse-dense gradient structure from the substrate surface toward the surface. The foam thus obtained was a product having a soft feel, a rich sense of volume, and light weight and excellent workability.

When the bonding strength between the base material and the synthetic resin foam was measured for the obtained product by the method described below, the product was a product in which both were firmly bonded.

Using a glue such as starch glue or synthetic glue used in the construction of conventional wallpaper for the product, a wall surface foundation, for example, plywood,
It is joined to gypsum board, mortar, concrete or asbestos slate board, etc., and after the adhesive is dried and solidified, the wallpaper is peeled off from the wall surface base. The wallpaper could be reconstructed without any adhesion of the residue and without adjusting the groundwork, and the workability was excellent.

Example 2 A basis was made of a polyvinyl chloride resin composition of the following formulation C containing a basis weight of 90 / m ² polyester nonwoven fabric (manufactured by Kurashiki Fiber Processing Co., Ltd., trade name: EX-3000) and further containing a foaming inhibitor. Solvent-type paint is applied using a gravure printing machine to a thickness of about 0.02 mm, and then dried in a heating furnace to form a uniform thin layer. The polyvinyl chloride resin composition of the following formulation D containing the above was laminated at a temperature of about 160 ° C. below the decomposition temperature of the foaming agent so as to have a thickness of about 0.20 mm to form a foamable synthetic resin layer. .

Formulation C: Polyvinyl chloride resin (= 700) (straight resin) 20 parts by weight MEK 90 parts by weight Toluene 30 parts by weight Ba-Zn stabilizer 1 part by weight Trimellitic anhydride (foaming inhibitor) 15 parts by weight Formulation D: Polyvinyl chloride resin (= 1100) (straight resin) 100 parts by weight DOP 65 parts by weight Ba-Zn stabilizer 3 parts by weight Azodicarboxylic acid amide (blowing agent) 5 parts by weight Filler 50 parts by weight Titanium white pigment 10 parts by weight Next, when the laminate is heated in a heating foaming furnace at about 210 ° C. for about 2 minutes, the foaming agent in Formulation D decomposes and foams, and at the same time, the foaming in Formulation C permeated into the vinyl chloride synthetic resin layer of Formulation D. Foaming is suppressed by the inhibitor, and a foam having the same coarse-dense gradient structure as in Example 1 is obtained. The product had soft feel, rich volume, and light weight and excellent workability. In addition, the above-mentioned product had the same bonding physical properties as in Example 1 and was rich in peelability with respect to the wall surface substrate.

Example 3 On the same substrate as in Example 1, a thin layer of the same synthetic resin composition and an expandable synthetic resin were formed, and a beige woven pattern was printed thereon using a gravure printing machine. Further, an embossing roll machine was used to apply a textured squeezed pattern, and a decorative material was obtained by the same processing method as in Example 1. This product was more versatile and rich in three-dimensional design than the product of Example 1, and had the same performance as the product of Example 1.

Comparative Example 1 A product comprising a synthetic resin foam was obtained in the same manner as in Example 1 except that the thin layer mixed with the foaming crosslinking agent of Example 1 was removed. In this product, the foaming is over-foamed as a whole, the structure of the foam cell is not obtained with a coarse / dense gradient, and because the foam cell is coarse, it peels off inside the foam layer, and the surface strength is weak, and the joint properties and actual A sufficient product could not be obtained by the peeling test of the above.

Comparative Example 2 A product consisting of a synthetic resin foam was obtained using exactly the same material and processing method as in Example 2 except that the thin layer mixed with the foaming inhibitor of Example 2 was removed. This product was inadequate in physical properties and performance as in Comparative Example 1.

The bonding strength between the base material and the synthetic resin foam layer thereon was measured by the following test method for the products obtained in Examples 1 and Comparative Example 2 described above.

(Test method) Each obtained product and gypsum board were each 30mm wide and 13mm long.
Adjusted to 0mm shape, vinyl acetate synthetic resin glue to one side length so as to be 30 g / m ² as a resin solid content of the plasterboard plates
It was applied to a thickness of 100 mm, and a cutting test of the product was placed thereon and adhered, and then left at room temperature for 7 days to completely dry the paste, thereby obtaining a test piece.

Next, the terminal of each of the test pieces was fixed to a chuck of a constant load tensile tester, and the chuck holding the gypsum board was lowered at a speed of 200 mm / min in an atmosphere at room temperature of 20 ° C. and a humidity of 65%. Measure the joint strength per length. The results were as follows.

[Effects] As described above, the present invention forms a synthetic resin thin layer mixed with a foaming crosslinking agent or a foaming inhibitor on a base material, and laminates a foamable synthetic resin layer on the synthetic resin thin layer to form a foamable synthetic resin layer. Resin foam cells can be formed into a foam having a dense-dense gradient structure, and therefore, while having high foaming, the joining strength between the base material and the synthetic resin foam can be significantly improved, and re-application such as re-placing Not only can be made simple and easy, but also obtain a superior product that has a soft touch, rich volume and high three-dimensional design, and is lightweight and has good workability. be able to.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view before foaming which is an embodiment of the present invention, and FIG. 2 is a cross-sectional view similarly after foaming. 1: Base material, 2: Thin layer, 3: Foamable synthetic resin layer, 4: Stretch pattern,
5: Print pattern.

Continuation of front page (56) References JP-A-55-97950 (JP, A) JP-A-61-225224 (JP, A) JP-A-63-118245 (JP, A) (58) Fields investigated (Int) .Cl. ⁶ , DB name) B32B 1/00-35/00 E04F 13/00-13/18

Claims (1)

(57) [Claims] (1) After forming a synthetic resin composition mixed with a foaming crosslinking agent or a foaming inhibitor on a substrate as a smooth and uniform thin layer, a foamable synthetic resin layer is further laminated on the layer.
Then, the foamed synthetic resin layer was heated and foamed to infiltrate the foamable cross-linking agent or foaming inhibitor into the foamable synthetic resin layer, and the foamable synthetic resin layer was formed from large bubbles to micro bubbles in order from the surface to the substrate surface. A method for producing a foamed decorative material, characterized in that the foamed decorative material is formed into a foam having a gradient structure.