JP2015124317A - Vinyl chloride resin for paste processing and vinyl chloride resin composition for paste processing using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin for paste processing which is capable of giving a foam having a good hue by suppressing coloring caused during processing, and to provide a vinyl chloride resin composition for paste processing obtained therefrom.SOLUTION: The vinyl chloride resin for paste processing contains 1-4,000 ppm of perchlorates. The vinyl chloride resin composition for paste processing is obtained from the vinyl chloride resin for paste processing.

Description

  The present invention relates to a vinyl chloride resin for paste processing (hereinafter sometimes abbreviated as “paste vinyl chloride”) and a paste vinyl chloride composition obtained therefrom, and more specifically, suppresses coloring that occurs during processing and has a good hue. The present invention relates to a paste vinyl chloride that gives a plastisol that can obtain a foam having the above and a paste vinyl chloride composition obtained therefrom.

  Paste PVC is generally processed as paste PVC sol by kneading with compounding agents such as plasticizers, stabilizers and foaming agents, and various molded products are obtained by various processing methods. Among them, building materials such as wallpaper, flooring and foam sheets are one of the main uses of paste PVC.

  In general, wallpaper, flooring, foamed sheets, etc., are prepared by applying a paste vinyl chloride sol to a backing material such as flame retardant paper and heating, a printing process in which the original is colored by gravure printing, etc. Manufactured by a method comprising a foaming step of foaming by heating. The foam thus obtained is devised in each step in order to impart design properties, and various uneven patterns are applied. As a method for forming a concavo-convex pattern on the foam, a mechanical embossing method that presses a metal roll with undulations on the foam, a chemical embossing method that impregnates the foam control agent into the original fabric in the printing process, and a paste from a rotary screen on the original fabric Examples include a rotary screen method in which a PVC sol is extruded and transferred. Among these, the chemical embossing method causes the foaming inhibitor coating portion to be colored in a foaming process in which high-temperature treatment is performed, resulting in a reddish product and a loss of appearance. Therefore, a paste vinyl chloride sol that can obtain a foam having a good hue even after chemical embossing is desired, but the desired paste vinyl chloride sol has not yet been developed.

  Until now, various stabilizers have been developed to suppress foam coloring. Among them, a mixture with a lead compound or a cadmium compound shows excellent coloration suppression (see, for example, Patent Document 1), but the use of a lead compound or a cadmium compound tends to be restricted from the viewpoint of safety.

  Further, although the replacement with a calcium-zinc stabilizer having low toxicity and high safety is in progress (for example, refer to Patent Document 2), the coloring suppression effect is insufficient.

JP-A-8-109299 JP 2003-138082 A

  The present invention solves the above-mentioned problems, suppresses coloring that occurs during processing, which cannot be obtained with conventional paste vinyl chloride, and can provide a foam having a good hue, and paste vinyl chloride composition obtained therefrom The purpose is to provide.

  In view of the state of the prior art as described above, the present inventors obtain a paste PVC that can suppress the coloration that occurs during processing and can obtain a foam having a good hue, and a paste PVC composition that is obtained therefrom. As a result of intensive studies, it was found that the intended paste PVC and a paste PVC composition obtained therefrom can be obtained by using a specific additive, and the present invention has been completed. That is, the present invention is a vinyl chloride resin for paste processing characterized by containing 1 to 4000 ppm of perchlorates.

  Hereinafter, the present invention will be described in detail.

  The paste vinyl chloride of the present invention contains 1 to 4000 ppm of perchlorates. When the content is less than 1 ppm, the coloring suppression effect is insufficient. On the other hand, when it exceeds 4000 ppm, the sol is thickened and the processability is lowered, and the foam suppression portion (concave portion) is yellowed. Since a foam suitable for processing can be obtained and a foam having a good hue can be obtained, the content is preferably 300 to 1800 ppm, and more preferably 500 to 1500 ppm.

  Here, examples of perchlorates include metal perchlorate, ammonium perchlorate, and the like. Examples of the metal constituting the metal salt include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, and zinc.

  The paste vinyl chloride of the present invention is a polymerization initiator, an emulsifier, an emulsification aid, a buffer, a higher alcohol, a higher fatty acid, a higher fatty acid ester, a dispersion aid such as chlorinated paraffin, and the like in the polymerization of paste vinyl chloride such as a polymerization degree adjuster. In addition, a generally added substance or the like may be contained.

  The paste vinyl chloride of the present invention is a vinyl chloride resin latex obtained by obtaining a vinyl chloride resin latex by a general emulsion polymerization method, micro suspension polymerization method, seed emulsion polymerization method, seed micro suspension polymerization method, etc. In addition, 0.0001 to 0.4 parts by weight of perchlorates can be added to 100 parts by weight of the vinyl chloride resin, and then water can be removed for production.

  Examples of the method for removing moisture from the vinyl chloride resin latex include spray drying, fluidized bed drying, aeration drying, rotary drying, conductive heating drying, and the like. A method by drying is preferred.

  The seed microsuspension polymerization method is shown below as an example of a method for obtaining a vinyl chloride resin latex used in producing the paste vinyl chloride of the present invention.

  The seed micro-suspension polymerization method is 1) the first step of obtaining a vinyl chloride resin seed latex containing a vinyl chloride resin containing an oil-soluble polymerization initiator by the micro suspension polymerization method, and 2) the obtained seed latex. The vinyl chloride monomer, or a monomer copolymerizable with vinyl chloride monomer, is polymerized with gentle stirring in the presence of deionized water, an emulsifier, a buffer, and if necessary, an emulsification aid such as higher alcohol. Is a polymerization method comprising a second stage in which the seed latex is enlarged to obtain a vinyl chloride resin latex.

  Here, examples of the monomer copolymerizable with the vinyl chloride monomer include vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, vinyl benzoate, acrylic acid, methacrylic acid, maleic acid, fumaric acid. Unsaturated carboxylic acid or anhydride thereof, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, maleic acid ester , Unsaturated carboxylic acid esters such as fumaric acid esters and cinnamic acid esters, vinyl ethers such as vinyl methyl ether, vinyl amyl ether and vinyl phenyl ether, monoolefins such as ethylene, propylene, butene and pentene, vinylidene chloride, Styrene and its Conductor, acrylonitrile, can be cited methacrylonitrile, etc. These vinyl monomers can be used with one or more.

  Examples of the emulsifier include alkyl sulfates such as sodium lauryl sulfate and myristyl sulfate, alkylaryl sulfonates such as sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate, dihexylsulfosuccinic acid. Sulfosuccinates such as sodium, fatty acid salts such as ammonium laurate and potassium stearate, anionic emulsifiers such as polyoxyethylene alkyl sulfates, polyoxyethylene alkylaryl sulfates, sorbitan monooleate, polyoxyethylene sorbitan mono Sorbitan esters such as stearate, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters Those conventionally known nonionic emulsifiers such as the like may be employed alone or in combination.

  Examples of the buffer include alkali metal monohydrogen phosphate, alkali metal dihydrogen phosphate, potassium hydrogen phthalate, sodium hydrogen carbonate, boric acid-caustic potassium solution, and the like.

  Examples of the emulsification aid used as necessary include higher alcohols such as cetyl alcohol and lauryl alcohol, higher fatty acids such as lauric acid, palmitic acid and stearic acid, esters thereof, aromatic hydrocarbons, higher fatty acid hydrocarbons, Examples thereof include halogenated hydrocarbons such as chlorinated paraffin.

  The seed latex used in the seed micro suspension polymerization method can be prepared by the following micro suspension polymerization method. First, add vinyl chloride monomer, oil-soluble polymerization initiator, surfactant, buffering agent, higher alcohol, higher fatty acid, higher fatty acid ester, dispersing aid such as chlorinated paraffin, and polymerization degree adjuster if necessary. Premix and homogenize with a homogenizer to adjust the oil droplets. As a homogenizer at this time, for example, a colloid mill, a vibration stirrer, a two-stage high-pressure pump, or the like can be used. Then, the homogenized liquid is sent to the polymerization vessel, the temperature in the polymerization vessel is raised while gently stirring to start the polymerization reaction, and the oil-soluble polymerization initiator is added by carrying out the polymerization until a predetermined conversion rate is reached. It is possible to adjust the contained seed latex.

  As the oil-soluble polymerization initiator, diacyl peroxide having a 10-hour half-life temperature of 30 to 70 ° C. is preferable. Examples of such a polymerization initiator include isobutyryl peroxide, 3,3,5-trimethylhexanoyl peroxide. Examples thereof include oxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, and succinic acid peroxide.

  When the paste vinyl chloride of the present invention is used as a paste vinyl chloride composition by blending a plasticizer, a filler, a foaming agent and the like, a good foam can be obtained. It is preferable to blend ~ 200 parts by weight, filler 300 parts by weight or less, and foaming agent 0.1-20 parts by weight.

  Examples of the plasticizer include bis (2-ethylhexyl) phthalate (hereinafter abbreviated as DOP), diisononyl phthalate, diisodecyl phthalate, dibutyl phthalate and the like, adipic acid (2-ethylhexyl), Adipic acid esters such as diisononyl adipate, trimellitic acid esters such as tri (2-ethylhexyl) trimellitic acid, triisodecyl trimellitic acid and trinormaloctyl trimellitic acid, tri (2-ethylhexyl) phosphate, phosphoric acid Phosphate esters such as tricresyl and trixylenyl phosphate, benzoic acid esters such as diethylene glycol dibenzoate and dipropylene glycol dibenzoate, other polyester plasticizers, sebacic acid esters, mazelineic acid esters, maleic acid esters Epoxidized vegetable oil, it can generally be used those which are used as plasticizers.

  Examples of the filler include calcium carbonate, diatomaceous earth, magnesium carbonate, and titanium oxide.

  Examples of foaming agents include inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, amide compounds, sodium borohydride, isocyanate compounds, azodicarbonamide, azobisisobutyronitrile, barium. Azo compounds such as azodicarboxylate, hydrazine derivatives such as p, p′-oxybisbenzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, semicarbazide compounds, azides, nitroso compounds such as dinitrosopentamethylenetetramine, triazole compounds, etc. An organic foaming agent is mentioned. And it is also possible to use together the said foaming agent and decomposition accelerators, such as zinc white (zinc oxide), as needed.

  In addition, a stabilizer may be used in combination, and examples of the stabilizer include an epoxy stabilizer, a barium stabilizer, a calcium stabilizer, a tin stabilizer, and a zinc stabilizer. Commercially available composite stabilizers such as calcium-zinc and barium-zinc can also be used.

  Furthermore, in addition to paste PVC, plasticizer, filler, and foaming agent, which are essential components for the paste PVC composition of the present invention, it is usually added to the paste PVC composition within a range not exceeding the object of the present invention. Additives such as antioxidants, flame retardants, thickeners, lubricants, UV absorbers, pigments and other colorants, surfactants, antistatic agents, etc. may be added, and their blending amounts are generally It does not matter as long as it is used.

  The paste PVC of the present invention can suppress the coloration that occurs during processing, and can obtain a foam having a good hue, and its industrial value is very high.

  Next, the content of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these.

<Average particle size>
Using a laser diffraction / scattering particle size distribution measuring apparatus (Horiba, Ltd., trade name LA-700), measurement was performed twice under the condition of a refractive index of 1.3 to obtain an average particle diameter.

<Measurement of initiator content in seed latex>
The seed latex was weighed in a 200 mL Erlenmeyer flask so that the vinyl chloride resin solid content would be 1 g. Subsequently, 20 mL of benzene, 80 mL of isopropyl alcohol, 20 mL of 10% acetic acid solution, and 20 mL of 10% aqueous potassium iodide solution were added. A five-ball condenser was attached to the Erlenmeyer flask, heated with stirring with a stirrer for 15 minutes, cooled, and titrated with 1 / 100N sodium thiosulfate.

  The initiator content in the seed latex was calculated by the following formulas (1) and (2).

A = (V1−V2) / 1000 × (1 / 100N) × (1/2) (1)
(Where A is the number of moles of initiator in the seed latex, V1 is the titration of 1 / 100N sodium thiosulfate in the sample (mL), and V2 is the titration of 1 / 100N sodium thiosulfate in the blank. (ML), N represents the normality of 1 / 100N sodium thiosulfate.)
Initiator content in vinyl chloride resin (%) = A / W × 398 × 100 (2)
(In the formula, W represents a seed solid content (g) containing an initiator, etc.)
<Method for evaluating the hue of the foam>
A ^* and b ^* were measured with a color difference meter (trade name MODEL-9463, manufactured by Nippon Denshoku). a ^* is an index representing redness, and the smaller the value of a ^* , the less redness of the foam. b ^* is an index representing yellowness, and the smaller the value of b ^* is, the less yellow the foam is.

Synthesis example 1
A 1 m ³ stainless steel autoclave was charged with 360 kg of deionized water, 300 kg of vinyl chloride monomer, 5.7 kg of lauroyl peroxide and 30 kg of a 15 wt% sodium dodecylbenzenesulfonate aqueous solution, and circulated for 3 hours using a homogenizer for homogenization. Thereafter, the temperature of the reaction system was raised to 45 ° C. to initiate polymerization. After the pressure of the polymerization system is reduced, the unreacted vinyl chloride monomer is recovered, and the solid content is 35% by weight, the average particle diameter is 0.55 μm, and the seed contains 2% by weight of lauroyl peroxide based on the polymer. Latex was obtained.

Example 1
In a 2.5 L stainless steel autoclave, 650 g of deionized water, 550 g of vinyl chloride monomer, 5.5 g of 5 wt% sodium dodecylbenzenesulfonate, 11.0 g of 1 wt% boric acid-caustic potassium solution, obtained by Synthesis Example 1 6.5 parts by weight of a seed latex having an average particle size of 0.55 μm was added to 100 parts by weight of the vinyl chloride monomer, and the temperature of the reaction mixture was raised to 52 ° C. to initiate polymerization. From the start of the polymerization to the end of the polymerization, 0.75 parts by weight of 5% sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. The polymerization was stopped when the polymerization pressure dropped from the saturated vapor pressure of the vinyl chloride monomer at 52 ° C. to 0.569 MPa, and the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride resin latex.

  To the obtained vinyl chloride resin latex, 0.25 g of sodium perchlorate (0.05 parts by weight with respect to 100 parts by weight of vinyl chloride resin) was added and stirred, using a rotary disk type spray dryer, Spray drying was performed at a hot air temperature of 158 ° C. and an outlet temperature of 55 ° C. to obtain paste vinyl chloride (content of sodium perchlorate: 500 ppm).

  For 100 parts by weight of the obtained paste PVC, 40 parts by weight of DOP as plasticizer (J Plus Co., Ltd., grade industry), and calcium carbonate as the filler (Nitto Flour Industry Co., Ltd., trade name NN # 500) ) 55 parts by weight, titanium oxide (Taika Co., Ltd., trade name JR600A) 45 parts by weight, foaming agent (Otsuka Chemical Co., Ltd., trade name AZ Ultra 1050) 5 parts by weight, zinc oxide (Daikyo Kasei Co., Ltd.) ), 2 parts by weight of trade name MZ-100), 2 parts by weight of stabilizers (ADEKA, O-130P), 3 parts by weight of thickener (BIC Chemie Japan, trade name BYK4041). Was used to knead to obtain a paste vinyl chloride composition.

The obtained paste PVC composition was coated on a flame retardant paper previously heated at 170 ° C. for 5 seconds at a thickness of 0.35 mm, and heated at 170 ° C. for 12 seconds to create a semi-gelled sheet, On the sheet, a 15% by weight solution of trimellitic anhydride / methyl ethyl ketone was applied as a foam inhibitor using a desktop gravure printing machine, gravure printed, and the foam inhibitor was infiltrated into the resin layer. Thereafter, foaming was performed by heating in an oven heated to 200 ° C. for 100 seconds to obtain a foam subjected to chemical embossing treatment. As a result of evaluating the foamed hue, the hue was a ^* of −0.54, b ^* Was 15.58 and it was a favorable hue.

Example 2
The amount of sodium perchlorate added was changed to 0.5 g (0.1 parts by weight with respect to 100 parts by weight of vinyl chloride resin), and other than that, paste vinyl chloride (containing sodium perchlorate was contained) in the same manner as in Example 1. the amount: 1000 ppm), to obtain a paste PVC composition to form a foam, the results of evaluating the foamed hue, hue ^{a *} is -1.08, ^{b *} is next 15.82 was good hue.

Example 3
The amount of sodium perchlorate added was changed to 0.75 g (0.15 parts by weight with respect to 100 parts by weight of vinyl chloride resin), and other than that, paste vinyl chloride (containing sodium perchlorate) was carried out in the same manner as in Example 1. the amount: 1500 ppm), to obtain a paste PVC composition, to prepare a foam, as a result of evaluating the foamed hue, hue ^{a *} is -1.85, ^{b *} is next 15.79 was good hue.

Example 4
The amount of sodium perchlorate added was changed to 1 g (0.2 parts by weight with respect to 100 parts by weight of the vinyl chloride resin), and other than that, paste vinyl chloride (sodium perchlorate content: 2000 ppm), a paste PVC composition was obtained, a foam was produced, and the foamed hue was evaluated. As a result, the hue was a ^* of -2.28 and b ^* of 16.01, which was a favorable hue.

Example 5
The amount of sodium perchlorate added was changed to 1.5 g (0.3 parts by weight with respect to 100 parts by weight of the vinyl chloride resin), and other than that, paste vinyl chloride (containing sodium perchlorate was contained) in the same manner as in Example 1. Amount: 3000 ppm), a paste vinyl chloride composition was obtained, a foam was produced, and the foamed hue was evaluated. As a result, the hue was a ^* of −2.65 and b ^* was 16.46, which was a favorable hue.

Example 6
The amount of sodium perchlorate added was changed to 2 g (0.4 parts by weight with respect to 100 parts by weight of the vinyl chloride resin), and other than that, paste vinyl chloride (sodium perchlorate content: 4000 ppm), to obtain a paste PVC composition, to prepare a foam, as a result of evaluating the foamed hue, hue ^{a *} is -2.77, ^{b *} is next 17.43 was good hue.

Comparative Example 1
A paste vinyl chloride (content of sodium perchlorate: 0 ppm) and paste vinyl chloride composition were obtained in the same manner as in Example 1 except that sodium perchlorate was not added, and a foam was produced and the foam hue was evaluated. As for hue, a ^* was 1.17 and b ^* was 15.15, which was a reddish hue.

Comparative Example 2
The amount of sodium perchlorate added was changed to 2.25 g (0.45 parts by weight with respect to 100 parts by weight of vinyl chloride resin), and other than that, paste vinyl chloride (containing sodium perchlorate) was carried out in the same manner as in Example 1. Amount: 4500 ppm), obtaining a paste vinyl chloride composition, producing a foam, and evaluating the foamed hue, the hue was a ^* = − 2.51, b ^{* =} 21.32, a yellowish hue was.

Comparative Example 3
The amount of sodium perchlorate added was changed to 2.5 g (0.5 parts by weight with respect to 100 parts by weight of vinyl chloride resin), and other than that, paste vinyl chloride (containing sodium perchlorate was contained) in the same manner as in Example 1. Amount: 5000 ppm), obtaining a paste vinyl chloride composition, producing a foam, and evaluating the foamed hue, the hue was a ^* = 2.15, b ^* 24.96, a yellowish hue was.

Comparative Example 4
Except for changing sodium perchlorate to sodium thiosulfate, paste vinyl chloride (sodium thiosulfate content: 500 ppm) and paste vinyl chloride composition were obtained in the same manner as in Example 1 to produce a foam, and the foam hue was changed. As a result of evaluation, hue ^{a *} is 1.21, ^{b *} was a hue tinged next to 15.53, the redness.

Comparative Example 5
A paste PVC (sodium sulfite content: 500 ppm) and a paste PVC composition were obtained in the same manner as in Example 1 except that sodium perchlorate was changed to sodium sulfite, a foam was prepared, and the foam hue was evaluated. As a result, a ^* was 1.06 and b ^* was 15.24, which was a reddish hue.

  The vinyl chloride resin for paste processing of the present invention can obtain a foam having a good hue even after chemical embossing, and is expected to be widely used for wallpaper, flooring, foam sheets, etc. Yes.

Claims (2)

A vinyl chloride resin for paste processing, which contains 1 to 4000 ppm of perchlorates. A plasticizer 20 to 200 parts by weight, a filler 300 parts by weight or less, and a foaming agent 0.1 to 20 parts by weight are blended with 100 parts by weight of the vinyl chloride resin for paste processing according to claim 1. A vinyl chloride resin composition for paste processing.