JP2003171494A - Method for preventing blocking of foamed decorative material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for preventing blocking of a material including a plasticizer with a foamed decorative material which is obtained by foaming a composition containing an aqueous emulsion containing a synthetic resin as an active ingredient, a foaming agent and an inorganic filler. <P>SOLUTION: The method for preventing blocking of the foamed decorative material and the material containing the plasticizer characteristically uses the decorative material obtained by foaming the aqueous emulsion using a synthetic resin as the active ingredient, a foaming agent and an inorganic filler, the synthetic resin comprises a ≤7C monomer unit as the principal component, and the aqueous emulsion contains ≥50 wt.% of toluene insoluble content. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing the foaming decorative material and a plasticizer-containing material from blocking. Specifically, an aqueous emulsion containing a synthetic resin such as an ethylene-vinyl ester polymer as an active ingredient, a foaming agent, and a foaming cosmetic material obtained by foaming a composition containing an inorganic filler, and a plasticizer-containing material A method for preventing blocking.

[0002]

2. Description of the Related Art A foaming decorative material obtained by foaming a composition containing an aqueous emulsion containing a synthetic resin as an active ingredient, a foaming agent and an inorganic filler, for example, the synthetic resin is an ethylene-vinyl ester polymer. In this case, it is reported in JP-A-7-188502.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have examined a laminate comprising a plasticizer-containing material of a vinyl chloride sheet containing a plasticizer such as phthalate ester and the foamed decorative material described in the above publication. However, it was found that the plasticizer-containing material and the foamed cosmetic material may be blocked, and it is clear that the cause of the blocking is that the plasticizer migrates from the plasticizer-containing material to the foamed cosmetic material. did. An object of the present invention is to provide a method for preventing blocking of a foaming cosmetic material obtained by foaming a composition containing an aqueous emulsion containing a synthetic resin as an active ingredient, a foaming agent and an inorganic filler, and a plasticizer-containing material. It is to be.

[0004]

[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have conducted extensive studies on an aqueous emulsion, and as a result, the synthetic resin, which is the active ingredient of the aqueous emulsion, is a monomer having a specific carbon number or less. By using an aqueous emulsion containing a unit as a main component and having a toluene insoluble content of the aqueous emulsion in a specific amount or more, blocking between the foamed cosmetic material obtained from the aqueous emulsion and the plasticizer-containing material is prevented. That is, the present invention has been completed.

That is, the present invention is a foaming decorative material obtained by foaming an aqueous emulsion containing a synthetic resin as an active ingredient, a foaming agent, and an inorganic filler, wherein the synthetic resin is a monomer having 7 or less carbon atoms. It is a synthetic resin containing units as the main component, and the toluene insoluble content of the aqueous emulsion is 50
A method for preventing blocking between a foam decorative material and a plasticizer-containing material, which comprises using a foam decorative material in an amount of at least wt%.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The aqueous emulsion used in the present invention is an aqueous emulsion in which a synthetic resin containing a monomer unit having 7 or less carbon atoms as a main component is used as an active ingredient, and the toluene insoluble content of the aqueous emulsion is 50% by weight or more. is there. Here, the monomer unit represents a portion corresponding to the raw material monomer used in the synthetic resin, and the synthetic resin is ethylene.
Explaining the vinyl acetate copolymer as a specific example, since the copolymer is obtained by copolymerizing ethylene and vinyl acetate, the monomer units of the copolymer are ethylene unit and vinyl acetate. The ethylene unit is a unit represented by the following general formula (1) among the copolymers. Is a structural unit represented by and has 2 carbon atoms. In addition, the vinyl acetate unit of the copolymer means the following general formula (2) among the copolymers. Is a structural unit represented by and has 4 carbon atoms.

The synthetic resin used in the present invention has 7 carbon atoms.
It has the following monomer units as its main components and has 7 carbon atoms.
The specific content of the following monomer units is 100 parts by weight of all the monomer units constituting the synthetic resin,
Usually, about 85 parts by weight or more, preferably about 95 parts by weight or more, and particularly preferably, substantially all the monomer units preferably have 7 or less carbon atoms.

The toluene insoluble content of the aqueous emulsion containing the synthetic resin used in the present invention is 50% by weight or more, preferably about 50 to 90% by weight. Here, the toluene-insoluble matter was obtained by applying an aqueous emulsion to a substrate and drying it, extracting 1 g of the obtained synthetic resin film with 100 cc of toluene at 90 ° C. for 2 hours, and then collecting and filtering with a 300-mesh wire net. It can be determined by measuring the amount of insoluble matter.

Examples of the synthetic resin which is an active ingredient of the aqueous emulsion used in the present invention include vinyl acetate polymers, ethylene-vinyl ester polymers, acrylic polymers, vinyl chloride polymers and vinylidene chloride polymers. Examples thereof include polymers, polyurethanes, polyesters, epoxy resins, silicone resins, polybutene, polybutadiene, butadiene-based copolymers, polyisoprene, polychloroprene, and polysulfide rubber. 2 as an aqueous emulsion
More than one kind of synthetic resin may be used as the active ingredient. Among the aqueous emulsions, polyurethane, ethylene-
An aqueous emulsion containing a vinyl ester polymer or an acrylic polymer as an active ingredient is preferable, and an aqueous emulsion containing an ethylene-vinyl ester polymer as an active ingredient is particularly preferable.

An aqueous emulsion containing an ethylene-vinyl ester polymer as an active ingredient will be described in more detail. An ethylene-vinyl ester polymer obtained by polymerizing ethylene and vinyl ester is used as an active ingredient. As the content of ethylene units contained in the ethylene-vinyl ester polymer, the polymer 1
The amount is 5 to 35 parts by weight, preferably 10 to 30 parts by weight, relative to 00 parts by weight. When the content of the ethylene unit is 5 parts by weight or more, the crack resistance and foaming property of the obtained foam decorative material tend to be improved, which is preferable, and when the content is 35 parts by weight or less, it is obtained. It is preferable because the foamed decorative material tends to have improved mechanical strength and blocking resistance.

The vinyl ester unit contained in the ethylene-vinyl ester polymer usually has 7 carbon atoms.
The following vinyl ester units are exemplified, and specific vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate and the like. As a vinyl ester unit,
You may contain 2 or more types of different vinyl ester units. Among the vinyl ester units, vinyl acetate units are preferred. The content of the vinyl ester unit contained in the ethylene-vinyl ester polymer is usually 65 to 95 parts by weight based on 100 parts by weight of the polymer.

As the monomer used in the ethylene-vinyl ester polymer, a (meth) acrylic acid ester having about 7 or less carbon atoms may be used. Here, as the (meth) acrylic acid ester, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc. Is mentioned. The content of the (meth) acrylic acid ester unit contained in the ethylene-vinyl ester polymer is usually 30 parts by weight or less, preferably 25 parts by weight or less, relative to 100 parts by weight of the polymer. Is.

A monomer copolymerizable with ethylene and having about 7 or less carbon atoms, which is a monomer other than ethylene, vinyl ester and acrylic acid ester (hereinafter referred to as a copolymerizable monomer) is ethylene- You may use as a raw material monomer of a vinyl ester polymer. Here, as the copolymerizable monomer, for example, acrylic acid, methacrylic acid,
Carboxyl group-containing monomers such as crotonic acid, itaconic acid (including half ester), maleic acid (including half ester) or anhydrides thereof; N-methylol derivative monomers such as N-methylol acrylamide; 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, mono (meth) of polyhydric alcohol
Hydroxy group-containing monomers such as acrylates; amino group-containing monomers such as dimethylaminoethyl methacrylate and dimethylaminopropyl acrylamide; epoxy group-containing monomers such as glycidyl (meth) acrylate; amide group-containing monomers such as acrylamide, methacrylamide, and maleinamide; Examples thereof include sulfo group-containing monomers such as sodium vinyl sulfonate, sodium methallyl sulfonate, and sodium 2-acrylamido-2-methylpropane sulfonate; and ethylene glycol diacrylate. The content of the ethylene-copolymerizable monomer unit contained in the ethylene-vinyl ester polymer is usually 10 with respect to 100 parts by weight of the polymer.
It is less than or equal to parts by weight.

The method for producing an aqueous emulsion containing a synthetic resin as an active ingredient used in the present invention includes, for example,
A method of dispersing a synthetic resin in water together with an emulsifying dispersant; an emulsion polymerization method of polymerizing in water in the presence of an emulsifying dispersant; an aqueous emulsion containing the synthetic resin obtained by emulsion polymerization as an active ingredient, and further (meth) acrylic. Examples thereof include a method of copolymerizing acids and the like. As a method for producing an aqueous emulsion, an emulsion polymerization method is preferable, and among them, an average degree of polymerization of 200 to 3,000 as a protective colloid of an emulsion dispersant.
The method of emulsion polymerization using polyvinyl alcohol of about 250 to 2500 is preferable.

The composition for foaming cosmetics used in the present invention can be obtained by mixing the above-mentioned aqueous emulsion, foaming agent and inorganic filler. Examples of the foaming agent include heat-expandable hollow microspheres. The heat-expandable hollow microspheres are a foaming agent composed of microspheres that can be expanded / foamed by heating.For example, polyacrylonitrile, acrylonitrile-methyl acrylate copolymer, etc. , Propane, butane, pentane, hexane,
Particle size 1 to 50 containing low boiling point hydrocarbons such as heptane
Examples thereof include spheres having a size of about μm, preferably about 2 to 30 μm.

The foaming starting temperature of the foaming agent is usually about 120 to 180 ° C. When the temperature is 120 ° C. or higher, foaming tends to be suppressed when the foaming cosmetic composition is dried, foaming of the foaming agent does not occur before the foaming layer is dried, and good after heat foaming. It is preferable because a foamed product can be easily obtained. Further, when the temperature is 180 ° C. or lower, the foamability tends to improve and the heating temperature at the time of foaming tends to decrease, which is preferable. As the foaming agent, for example, a commercially available foaming agent such as "Microsphere" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. can be used.

The content of the foaming agent in the foaming cosmetic composition is usually about 3 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the solid content of the aqueous emulsion. is there. When the content of the foaming agent is 3 parts by weight or more, the surface strength of the obtained foamed decorative material tends to be improved, and when it is 30 parts by weight or less, the expansion ratio tends to be improved, which is preferable. .

The inorganic filler used in the present invention is, for example, aluminum hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, ferrous hydroxide, basic zinc carbonate, Examples include basic lead carbonate, silica sand, clay, talc, silicas, titanium dioxide, magnesium silicate and the like. Among them, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, first hydroxide
Iron, basic zinc carbonate and basic lead carbonate are preferred.

The content of the inorganic filler in the foamed cosmetic material composition is 1% of the solid content of the aqueous emulsion.
It is usually about 50 to 300 parts by weight, preferably 50 to 250 parts by weight, relative to 00 parts by weight. If the content of the inorganic filler is 50 parts by weight or more, the flame-retardant property of the foamed decorative material obtained tends to be improved, and if it is 300 parts by weight or less, the mechanical strength and crack resistance of the foamed decorative material obtained are increased. It is preferable because the property tends to be improved.

The composition for foamed cosmetics used in the present invention may contain additives such as colorants, dispersants, antiblocking agents, defoamers and thickeners.

The foamed decorative material used in the present invention is obtained by coating the composition for foamed decorative material thus obtained on a sheet such as paper or a synthetic resin film and foaming the composition. Examples of the coating method for a sheet for obtaining the material include coating methods such as knife coater, nozzle coater, gravure coater, rotary screen coater, and reverse roll coater. Further, a pattern pattern may be printed on the surface of the material by a gravure printing method, an offset printing method, a screen printing method or the like with a foaming ink, a non-foaming ink or the like containing an aqueous emulsion as a main component.

The present invention provides a method for preventing the foamed decorative material thus obtained and the plasticizer-containing material from blocking, and a laminated body comprising the foamed cosmetic material and the plasticizer-containing material with reduced blocking. is there. When the foamed cosmetic material described above is used, the amount of the plasticizer transferred from the plasticizer-containing material to the foamed cosmetic material is significantly reduced. Therefore, the foamed cosmetic material and the plasticizer-containing material are treated under normal pressure or pressure. It is possible to prevent blocking even when it is brought into contact with.

Here, the plasticizer-containing material is one containing a plasticizer as an essential component, and examples thereof include those containing a plasticizer and a thermoplastic resin. As a plasticizer,
For example, phthalates such as dibutyl phthalate, dioctyl phthalate and diisononyl phthalate; phosphates such as tricresyl phosphate; glycerols such as polyethylene glycol; fatty acid esters such as octyl adipate and octyl sebacate; chlorinated paraffins And so on. Further, as the thermoplastic resin, for example, carboxymethyl cellulose, methyl cellulose,
Examples include fibrin derivatives such as hydroxyethyl cellulose, cellulose acetate, nitrocellulose, and viscose; polyvinyl chloride and the like.

The plasticizer-containing material includes the above-mentioned inorganic filler,
Compounding agents such as pigments, glass fibers, antioxidants, weathering agents and antistatic agents may be contained. Specific examples of the plasticizer-containing material include commercially available vinyl chloride synthetic leather and vinyl chloride sheet.

[0025]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Parts and% in the examples mean weight basis unless otherwise specified. Further, the solid content of the present invention refers to JIS
It is an evaporation residue obtained by drying in accordance with 4.9 of K6828.

(Production Examples 1 to 4 of Foaming Cosmetic Composition) As the aqueous emulsion, ethylene-vinyl ester-based copolymer obtained by using ethylene, vinyl acetate and vinyl versatate (carbon number 8) as raw material monomers An aqueous emulsion containing coalesced as an active ingredient. Specifically, it is described in JP-A-7-
It was manufactured according to the example of 188502 publication. Table 1 shows the content ratios of ethylene units, vinyl acetate units, vinyl versatate units, and toluene insolubles contained in the obtained aqueous emulsion. Next, the composition was prepared by mixing in the weight ratios shown in Table 2.

(Example 1, Comparative Examples 1 to 3) Basis weight 100 g
Approximately 100 g of the composition for foaming decorative material on a flame-retardant paper of / m ²
(Solid content) / m ² so that 1 coat in oven
It was dried at 20 ° C for 2 minutes to obtain a base layer. Next, a pattern was formed on the base layer by gravure printing using a water-based ink, and then embossing was performed at 210 ° C. for 30 seconds to obtain a foam decorative material. A synthetic leather made of vinyl chloride (containing 60 parts of a plasticizer (dioctyl phthalate) per 100 parts of vinyl chloride resin) was laminated on the side of the obtained foamed cosmetic material coated with the composition for foamed cosmetic material. , 0.049MP
Pressurized at a for 12 hours. The blocking state of the obtained laminate is summarized in Table 1. The state of blocking was visually observed and classified as follows. ◯: When the laminate was lifted up, the foam decorative material and the synthetic leather were easily separated. Δ: Peeling occurred, but tack was generated on the surface of the foam decorative material, or when the laminate was lifted, the foam decorative material and the synthetic leather were not immediately separated. X: Peeling did not occur unless the foamed decorative material and the synthetic leather were separated by hand.

(Measurement of the amount of plasticizer transferred to the foamed decorative material)
The foamed decorative material was peeled off from the laminate obtained in the previous section, and 100
cm^TwoFinely cut the foamed cosmetic material of
These were ultrasonically extracted with 50 mL of chloroform (30
) And analyze it by gas chromatography to
Plasticizer contained in foamed cosmetics by quantifying dioctyl acetate
The amount was calculated. Next, fluororesin film (Toyofuron
(Toray Synthetic Film Co., Ltd.)) and vinyl chloride synthetic leather
Laminated leather (plasticizer: dioctyl phthalate), 0.04
After pressurizing at 9 MPa for 12 hours, the fluororesin fill
100cm after peeling off ^TwoFinely the film
Cut and sonicate these with 50 mL of chloroform.
Extract (30 minutes) and analyze by gas chromatography
Then, the amount of dioctyl phthalate was quantified.
The amount of plasticizer deposited on the surface of the material is 0.1%.
It was. Shifted from synthetic leather to foam cosmetics to foam cosmetics
The amount of plasticizer contained in the foamed cosmetic material
The value obtained by subtracting the amount of plasticizer adhered to the surface from the amount is shown in Table 1.
Posted.

[0029]

[Table 1]

[0030]

[Table 2] (Foam cosmetic composition)

[0031]

According to the present invention, it is possible to provide a method for preventing blocking even when a foamed decorative material comes into contact with a plasticizer-containing material or under pressure.

Continued front page    (72) Inventor Hideki Yamamoto             1-5-1 Taito, Taito-ku, Tokyo Toppan stamp             Imprint Co., Ltd. (72) Inventor Mitsuru Nakagawara             1-5-1 Taito, Taito-ku, Tokyo Toppan stamp             Imprint Co., Ltd. (72) Inventor Yasuo Kanajima             3-1,98-1 Kasugade, Konohana-ku, Osaka             Kaika Chemtex Co., Ltd. (72) Inventor Tatsuo Mitsutake             3-1,98-1 Kasugade, Konohana-ku, Osaka             Kaika Chemtex Co., Ltd. F-term (reference) 4F074 AA22 AC17 AC24 AC32 AG01                       BA91 DA24                 4F100 AA01A AK01A AK04A AK07A                       AK08A AK15 AK68 AT00B                       BA02 CA01 CA23 DJ04A                       EH46 EH462 EJ17 EJ172                       EJ39 EJ392 EJ86 EJ862                       GB08 GB48 GB81 JL14 JM01A

Claims (5)

[Claims] 1. A foaming decorative material obtained by foaming an aqueous emulsion containing a synthetic resin as an active ingredient, a foaming agent, and an inorganic filler, wherein the synthetic resin comprises a monomer unit having 7 or less carbon atoms as a main component. A method for preventing blocking between a foamed decorative material and a plasticizer-containing material, which is characterized by using a foamed decorative material which is a synthetic resin having a toluene insoluble content of 50% by weight or more in an aqueous emulsion. 2. A synthetic resin containing, as a synthetic resin, 85 parts by weight or more of a monomer unit having 7 or less carbon atoms based on 100 parts by weight of all the monomer units constituting the synthetic resin. The method of preventing blocking of claim 1, wherein the method is blocking. 3. The method for preventing blocking according to claim 1, wherein an ethylene-vinyl ester polymer is used as the synthetic resin. 4. A foaming cosmetic material obtained by foaming a composition containing 3 to 30 parts by weight of a foaming agent and 30 to 300 parts by weight of an inorganic filler with respect to 100 parts by weight of a solid content of an aqueous emulsion. A method for preventing blocking according to claim 1, wherein a cosmetic material is used. 5. A laminate obtained by laminating a foaming decorative material and a plasticizer-containing material, wherein the foaming decorative material is obtained by foaming an aqueous emulsion containing a synthetic resin as an active ingredient, a foaming agent and an inorganic filler. Laminated foamed decorative material, wherein the synthetic resin is a synthetic resin containing a monomer unit having 7 or less carbon atoms as a main component, and the toluene insoluble content of the aqueous emulsion is 50% by weight or more. body.