JP4402153B1 - Aqueous matte surface treating agent composition and polyvinyl chloride resin product having coating layer thereof - Google Patents

Abstract

The present invention provides an aqueous matte surface treatment composition that can be applied to vinyl chloride resin sheets, leather, tarpaulins and the like to form a matte film excellent in blocking resistance, antifouling property and adhesion.
In an aqueous emulsion of a methacrylic resin having a methyl methacrylate content of 70 parts by weight or more as a base resin, (B) average particles as a matting agent with respect to 100 parts by weight of the nonvolatile content of (A) An aqueous matte surface treating agent composition is obtained by blending 5 to 100 parts by weight of internally crosslinked organic fine particles having a diameter of 1 to 8 μm and 15 to 150 parts by weight of (C) an organic solvent as a film forming aid. This composition is applied to a vinyl chloride resin substrate and dried by heating to form a target film.
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Description

  The present invention relates to an aqueous treatment composition that protects the surfaces of a vinyl chloride resin sheet, leather, and tarpaulin and gives a matte appearance.

  In general, a vinyl chloride resin sheet prevents the plasticizer added to give flexibility from bleeding on the surface, causing stickiness and dirt adhesion. Surface treatment is carried out with a coating agent comprising

However, most of the conventional coating agents are solvent-based (Patent Documents 1 and 2). In recent years, efforts to make water-based have been promoted due to increased awareness of regulations on VOC emissions and improvement of the work environment, and inventions relating to aqueous treatment agents have also been reported (Patent Documents 3 and 4).
However, water-based urethane resins having many hydrophilic groups are used for these binders, causing a problem that they react with moisture in the atmosphere to cause hydrolysis and become sticky when used for a long time.

Moreover, although there exists an aqueous processing agent which uses (meth) acrylic-type resin for a binder like patent document 5, since it is a comparatively soft resin with Tg of 30-60 degreeC, a plasticizer bleed prevention effect and blocking resistance are also shown. It was not enough.
In the matte type, inorganic silica is generally used as a matting agent (Patent Document 6). However, inorganic silica has a low affinity with the binder resin, and even after the film is formed, a domain is formed between the silica and the binder, from which the plasticizer moves to the surface, and moisture in the atmosphere is absorbed by the film. The film softens.

In particular, when both surfaces of the sheet are surface-treated, there may be a problem that the overlapping films cause blocking, and the sheet wound after the treatment cannot be pulled out.
For these reasons, conventional aqueous treatment agents have inferior coating film performance as compared with solvent-based systems.

JP-A-4-39400 Japanese Patent Laid-Open No. 10-279843 JP 2005-344049 A JP 2007-319836 A JP 2006-274122 A JP 2007-262248 A

  An object of the present invention is to provide an aqueous surface treatment agent that gives a matte appearance, protects it from stickiness and contamination by a plasticizer such as a vinyl chloride resin sheet, and does not cause blocking.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has (B) crosslinked organic fine particles and (C) film formation in a methacrylic emulsion containing 70 parts by weight or more of (A) methyl methacrylate. The present inventors have found that a composition obtained by mixing an auxiliary agent can achieve the above-mentioned object, and have reached the present invention.

That is, the present invention is as follows.
(A) Methyl methacrylate- ethyl acrylate-acrylic acid ternary copolymer aqueous emulsion having a methyl methacrylate content of 70 parts by weight or more, and (B) silicone with respect to 100 parts by weight of the nonvolatile content of the aqueous emulsion An aqueous solution obtained by mixing 5 to 100 parts by weight of internally crosslinked organic fine particles having an average particle diameter of 1 to 8 μm selected from a resin or a fluororesin and (C) 15 to 150 parts by weight of a film-forming auxiliary. Matte surface treatment composition.
(2) The aqueous matte according to (1), wherein the glass transition point (Tg) of the terpolymer of (A) methyl methacrylate-ethyl acrylate-acrylic acid is 60 ° C. to 120 ° C. Surface treatment agent composition.

(3) The film-forming auxiliary (C) is at least one selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and N-methyl-2-pyrrolidone.
The aqueous matte surface treating agent composition according to (1) or (2), characterized in that it is of a kind.
(4) The aqueous matte surface treating agent composition according to any one of (1) to (3), wherein the surface treating agent composition is a surface treating agent for a polyvinyl chloride resin product.

(5) above (1) to (4) or with an aqueous matte-surface treatment composition according to, polyvinyl chloride resin sheet, characterized in that the formation of the matt film on the surface of the poly Vinyl chloride resin leather or polyvinyl chloride resin tarpaulin products.

  The above-mentioned aqueous matte surface treatment composition is applied to a vinyl chloride resin sheet or leather or tarpaulin product used for tents, track seats, furniture, interiors, etc. with a gravure coater, etc. By drying for ˜2 minutes, it is possible to form a film that is matte and that is protected from stickiness and contamination due to bleeding of the plasticizer added to the vinyl chloride resin on the surface and that does not cause blocking.

Hereinafter, the present invention will be described in detail.
First, the component (A) will be described. It is an aqueous emulsion in which a methacrylic resin is dispersed in water, and becomes a base of a film formed by heating and drying after coating.
The aqueous emulsion of (A) methacrylic resin is obtained by copolymerizing an ethylenically unsaturated monomer with a methyl methacrylate content of 70 parts by weight or more, preferably 80 parts by weight or more.

By containing 70 parts by weight or more of methyl methacrylate, the film has a high hardness and the blocking resistance is improved. If it is less than 70 parts by weight, the coating film becomes soft and the adhesion to the substrate and the followability are improved, but the blocking resistance and antifouling property are inferior.
The remaining ethylenically unsaturated monomers other than methyl methacrylate are methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, isopropyl methacrylate, methacrylic acid. N-butyl acid, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, hydroxypropyl methacrylate, 2-hydroxyl acrylate, hydroxypropyl acrylate, acrylic amide, methacrylamide, N-methylolacrylamide, glycidyl Examples thereof include methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, vinyl chloride, vinylidene chloride and the like.

  In addition, when 1 to 3 parts by weight of a monomer containing a carboxyl group such as acrylic acid, methacrylic acid, maleic acid or itaconic acid is blended, the polymerization stability and the storage stability of the obtained emulsion can be improved.

  In order not to lower the blocking resistance and the antifouling property, in addition to the methyl methacrylate content being 70 parts by weight or more, the Tg of the copolymer is preferably 60 to 120 ° C, and preferably 75 to 110 ° C. It is more preferable. When Tg is less than 60 ° C., blocking resistance and antifouling properties are lowered, and when Tg exceeds 120 ° C., adhesion does not occur at a normal drying temperature (80 to 150 ° C.).

(A) Although it does not specifically limit as a method to obtain the aqueous emulsion of a methacryl resin, The phase inversion method of neutralizing with an alkali after solution polymerization and disperse | distributing to water needs to introduce many hydrophilic functional groups into resin. The coating film easily absorbs external moisture.
Further, the molecular weight of the resin obtained by solution polymerization is relatively small, and the effect of preventing the surface migration of the plasticizer that bleeds out from the vinyl chloride resin sheet is poor. For this reason, emulsion polymerization is preferred as a method for obtaining an aqueous emulsion of (A) methacrylic resin.

  Emulsion polymerization may be performed by a general method, and the surfactant may be any one of anionic, cationic, and nonionic anionic surfactants having polyethylene oxide, or may be used in combination with a nonionic surfactant. A reactive emulsifier having an ethylenically unsaturated double bond in the molecule can also be used.

Next, the component (B) will be described.
(B) The internally crosslinked organic fine particles having an average particle diameter of 1 to 8 μm give a matte appearance by imparting irregularities to the coating film. Any resin that is internally cross-linked and does not melt by heat drying can be used. (Meth) acrylic resin, silicone resin, fluorine resin, urethane resin, (meth) acrylic-urethane copolymer resin, melamine resin, polyamide resin, epoxy resin , Polyethylene resin and polypropylene resin can be selected. Among these, (meth) acrylic resin is particularly effective because it has a high affinity with the binder, it is difficult to form a domain through which plasticizers from the vinyl chloride resin substrate and moisture and dirt from the outside pass, and it has excellent weather resistance. is there.

Crosslinked fine particles of (meth) acrylic resin can be obtained by suspension polymerization of (meth) acrylic monomer containing bifunctional or higher functional monomer. As a commercially available product, Art Pearl J-4P (manufactured by Negami Kogyo Co., Ltd .: average particle size 2.2 μm) can be used.
Other examples of commercially available crosslinked organic fine particles that can be used include 33 Additive (manufactured by Toray Dow Corning Co., Ltd .: average particle size 3 μm) for silicone resins, and SST-4MG (manufactured by SHAMROCK: particle sizes) for fluororesins. 2 to 4 μm). These are excellent in blocking resistance and antifouling properties, but are expensive.

In addition, art pearl C-800 transparent (manufactured by Negami Kogyo Co., Ltd .: average particle size 6 μm) can be used for urethane resin, and the coating film can be given a soft touch, which is effective for applications where the final product is touched .
In any case, the appearance can be changed depending on the particle diameter, but when the coating is applied with a gravure coater, the average particle diameter is preferably 1 to 8 μm. If it is less than 1 μm, the effect as a matting agent is small, and if it exceeds 8 μm, uneven coating or detachment from the coating film easily occurs.

  The addition amount is preferably 5 to 100 parts by weight, more preferably 15 to 40 parts by weight, based on the nonvolatile content of the aqueous methacrylic resin emulsion. If it is less than this, a matte appearance cannot be obtained, and if it is more than this, desorption from the coating film is likely to occur and the antifouling property is also lowered.

Next, the component (C) will be described.
(C) The film-forming auxiliary is a high-boiling organic solvent, and enables film formation at a low temperature by swelling an aqueous resin emulsion.

  Known alcohols such as t-butanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether Diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol Rudibutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol Glycol ethers such as dibutyl ether and 3-methyl-3-methoxybutanol, propylene glycol dimethyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol dipropyl ether acetate, propylene glycol dibutyl ether acetate, dipropylene glycol dimethyl ether acetate And glycol ether acetates such as dipropylene glycol diethyl ether acetate, dipropylene glycol dipropyl ether acetate and dipropylene glycol dibutyl ether acetate, and N-methyl-2-pyrrolidone.

  Actually, these have high water solubility, low odor, and low toxicity (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether) , Ethylene glycol dipropyl ether, ethylene glycol dibutyl ether and the like are considered to be highly toxic.) And stability (glycol ether acetates are easily hydrolyzed).

In the present invention, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether are preferred.
The addition amount is preferably 15 to 150 parts by weight, more preferably 25 to 100 parts by weight with respect to the nonvolatile content of the (A) methacrylic resin. If it is less than this, the adhesion to the substrate is poor, and if it is more, the drying speed is slow.

  In addition, additives such as a wetting agent, a thickening agent, an antifoaming agent, and an organic solvent can be added depending on the coating method.

The method for coating the surface treatment agent of the present invention on the substrate is not particularly limited, and can be performed by gravure coating, roll coating, knife coating, spray coating, brush coating, dipping, or the like. Then, a membrane | film | coat is formed by making it dry at 80-150 degreeC.
In the case of a gravure coat, it is preferable to apply 100 to 200 meshes once or twice.

Hereinafter, although a manufacture example, an Example, and a comparative example are demonstrated in detail, this invention is not limited to these.
(Methacrylic resin aqueous emulsion production example 1)
In the formulation shown in Table 1, it is obtained by ordinary emulsion polymerization. First, a well-mixed monomer was added to a pre-emulsion surfactant Monogen Y-100 (Daiichi Kogyo Seiyaku Co., Ltd.) and deionized water mixed and dissolved with a homogenizer, and the mixture was mixed at 5000 rpm. Stir for 5 minutes to make a pre-emulsion.

5 parts by weight of the pre-emulsion, surfactant Y-100 (Daiichi Kogyo Seiyaku Co., Ltd.) and deionized water were weighed into the flask, and the inside of the reaction vessel was replaced with nitrogen gas. While stirring at 200 rpm, the reaction vessel was heated to 70 ° C., and an ammonium persulfate (APS) aqueous solution as an initiator was added. The remaining pre-emulsion was supplied uniformly over 3 hours from 10 minutes after the initiator was charged, and the inside of the reaction vessel was kept at 70 ° C. during that time. After completion of the pre-emulsion supply, the temperature in the reaction vessel was raised to 75 ° C. and further reacted for 90 minutes.
After completion of the reaction, the flask was cooled to 30 ° C. or lower, and 15% aqueous ammonia was added to neutralize the pH to 7.5 to 8.5.

(Methacrylic resin aqueous emulsion production examples 2-3)
Reaction similar to the methacryl resin aqueous emulsion manufacture example 1 was performed except having replaced methyl methacrylate with ethyl acrylate in the mixing | blending shown in Table 1, and having changed the methyl methacrylate content rate to 73-63 weight part.

Example 1
Based on the formulation in Table 2, cross-linked acrylic fine particles (Art Pearl J-4P: manufactured by Negami Kogyo Co., Ltd.), a delustering agent for the nonvolatile content of the emulsion having a methyl methacrylate content of 83 parts by weight obtained in Production Example 1, Ionized water was added and stirred for 10 minutes at 200 rpm, and then a urethane thickener (Primal SCT-275: manufactured by Rohm and Haas) was added with dipropylene glycol monomethyl ether (Dawanol DPM: manufactured by Dow Corning) and isopropyl alcohol ( IPA: Shin Nippon Petroleum Co., Ltd.) and silicone-based wetting agent (FZ-77: manufactured by Toray Dow Corning) were added in this order and stirred for 10 minutes each to obtain an aqueous treatment agent having a solid content of 20%. .

(Example 2)
An aqueous treatment agent was obtained in the same manner as in Example 1 except that the aqueous methacrylic resin emulsion of Example 1 was changed to an emulsion having a methyl methacrylate content of 73 parts by weight obtained in Production Example 2.

(Example 3)
An aqueous treatment agent was obtained in the same manner as in Example 1 except that the matting agent of Example 1 was changed from crosslinked methacrylic fine particles to silicone rubber fine particles (33Additive: manufactured by Toray Dow Corning).

Example 4
An aqueous treatment agent was obtained in the same manner as in Example 1 except that the matting agent in Example 1 was changed from crosslinked methacrylic fine particles to fluororesin fine particles (SST-4MG: manufactured by SHAMROCK).

(Example 5)
An aqueous treatment agent was obtained in the same manner as in Example 1 except that the matting agent of Example 1 was changed from crosslinked methacrylic fine particles to urethane resin fine particles (Art Pearl C-800 transparent: manufactured by Negami Kogyo Co., Ltd.).

(Comparative Example 1)
An aqueous treatment agent was obtained in the same manner as in Example 1 except that the aqueous methacrylic emulsion of Example 1 was changed to an emulsion having a methyl methacrylate content of 63 parts by weight obtained in Production Example 3.

(Comparative Example 2)
The same as Example 1 except that the addition amount of dipropylene glycol monomethyl ether (Dawanol DPM: manufactured by Dow Corning) of Example 1 was changed to 7.5 parts by weight with respect to the nonvolatile content of the aqueous methacrylic resin emulsion. An aqueous treating agent was obtained by this method.

(Comparative Example 3)
The same method as in Example 1 except that the amount of dipropylene glycol monomethyl ether (Dawanol DPM: manufactured by Dow Corning) of Example 1 was changed to 225 parts by weight with respect to the nonvolatile content of the aqueous methacrylic resin emulsion. An aqueous treatment agent was obtained.

(Comparative Example 4)
Example 1 except that the matting agent of Example 1 was changed from crosslinked methacrylic fine particles having an average particle size of 2.2 μm to crosslinked methacrylic fine particles having an average particle size of 14 μm (Art Pearl G-400 transparent: manufactured by Negami Kogyo Co., Ltd.). An aqueous treatment agent was obtained in the same manner as above.

(Comparative Example 5)
The same method as in Example 1 except that the matting agent in Example 1 was changed from crosslinked methacrylic fine particles having an average particle size of 2.2 μm to powdered silica (TS-100: manufactured by Degussa) having an average particle size of 2.2 μm. An aqueous treatment agent was obtained.

(Comparative Example 6)
The addition amount of the cross-linked methacrylic fine particles (Art Pearl J-4P: manufactured by Negami Kogyo Co., Ltd.), which is the matting agent of Example 1, was changed from 43 parts by weight to 150 parts by weight with respect to the nonvolatile content of the methacrylic resin aqueous emulsion. Except for the above, an aqueous treatment agent was obtained in the same manner as in Example 1.

  The aqueous treatment agent obtained in Examples 1 to 5 and Comparative Examples 1 to 6 was applied to a vinyl chloride resin sheet with a 120 mesh gravure coater and dried in an oven at 120 ° C. for 2 minutes to form a film. It was.

  The evaluation methods of the blocking resistance, adhesion and antifouling property of the films by the aqueous treatment agents obtained in Examples 1 to 2 and Comparative Examples 1 to 5 are shown below.

(Blocking resistance)
Surface treated vinyl chloride resin sheet 5 × 5 cm square 2 treated surfaces are stacked and stacked for 10 days under a constant temperature and humidity chamber at a temperature of 60 ° C. and a humidity of 98% under a load of 10 kg. Peel and check for blocking.
○: It is not blocked or can be peeled off with very light force.
(Triangle | delta): Although it is blocking, it can peel when force is applied.
X: Cannot be peeled off due to blocking, or very strong force is required.

(Anti-fouling property)
50 parts by weight of cement, 38 parts by weight of humus, 10 parts by weight of machine oil, and 2 parts by weight of carbon black are mixed and stirred in artificially prepared dirt, and the adhesion of the dirt is visually confirmed.
○: Dirt hardly adheres.
Δ: Dirt adheres thinly.
X: Dirt adheres thickly.

(Adhesion)
A cellophane tape (CT-12 manufactured by Nichiban Co., Ltd.) is applied to the film formed on the vinyl chloride resin sheet, and the presence or absence of film peeling is checked visually when peeled off at once.
○: No peeling △: Partial peeling ×: All peeling

  Table 2 shows the compositions of Examples 1 to 5 and Comparative Examples 1 to 6 and the results of coating film performance evaluation.

As is clear from the results in Table 2, the coatings obtained from the aqueous treatment agents of Examples 1 to 5 were all good in blocking resistance, antifouling property and adhesion.
On the other hand, as in Comparative Example 1, as the methyl methacrylate content in the aqueous methacrylic resin emulsion decreases, the film becomes softer and the blocking resistance and antifouling properties are reduced.

As in Comparative Example 2, if the addition amount of the film-forming aid is insufficient, a dense film is not obtained, and adhesion, antifouling properties and anti-blocking properties are inferior.
As in Comparative Example 3, when the amount of the film-forming auxiliary added is too large, the solvent remains in the coating film even after drying, and the blocking resistance and antifouling property are lowered.
As in Comparative Example 4, when the particle size of the matting agent is large, the portion protruding from the coating film increases and the adhesion is poor.

When powdered silica is used for the matting agent as in Comparative Example 5, the affinity with the binder resin is poor and the blocking resistance and antifouling properties are reduced.
If the amount of the matting agent added to the non-volatile content of the aqueous emulsion is 100% or more as in Comparative Example 6, the matting agent has insufficient fixing force and is detached from the film.

  INDUSTRIAL APPLICABILITY The present invention can provide an aqueous surface treating agent that gives a matte appearance, protects it from stickiness and contamination by a vinyl chloride resin sheet, leather, and tarpaulin plasticizer and does not cause blocking.

Claims (5)

(A) Methyl methacrylate- ethyl acrylate-acrylic acid ternary copolymer aqueous emulsion having a methyl methacrylate content of 70 parts by weight or more, and (B) silicone with respect to 100 parts by weight of the nonvolatile content of the aqueous emulsion An aqueous solution obtained by mixing 5 to 100 parts by weight of internally crosslinked organic fine particles having an average particle diameter of 1 to 8 μm selected from a resin or a fluororesin and (C) 15 to 150 parts by weight of a film-forming auxiliary. Matte surface treatment composition. 2. The aqueous matte surface treating agent according to claim 1, wherein the ternary copolymer of (A) methyl methacrylate-ethyl acrylate-acrylic acid has a glass transition point (Tg) of 60 ° C. to 120 ° C. 3. Composition. The (C) film forming aid is at least one selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and N-methyl-2-pyrrolidone. The aqueous matte surface treating agent composition according to claim 1 or 2.   The aqueous matte surface treating agent composition according to any one of claims 1 to 4, wherein the surface treating agent composition is a surface treating agent for a polyvinyl chloride resin product. A sheet made of a polyvinyl chloride resin, wherein a matte film is formed on the surface using the aqueous matte surface treating agent composition according to any one of claims 1 to 5, and a polyvinyl chloride resin Tarpaulin products made of leather or polyvinyl chloride resin .