JP2022151172A - Polyvinyl chloride-based paste resin and resin composition for automobile primer - Google Patents

Abstract

To provide a polyvinyl chloride-based paste resin that gives paste sol having excellent slip resistance.SOLUTION: According to one embodiment, a polyvinyl chloride-based paste resin contains a polyvinyl chloride polymer and a polymerization emulsifier. Relative to 100 pts.wt. of the polyvinyl chloride polymer, the amount of the polymerization emulsifier is more than 0.30 pt.wt. to 0.50 pt.wt or less.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a vinyl chloride paste resin and a resin composition for automobile undercoat.

Vinyl chloride-based paste resins are used in a variety of applications including automotive primers, flooring, gloves, toys, and the like. Vinyl chloride paste resins are used by being mixed with a plasticizer or the like to form a paste sol.

For example, Patent Document 1 discloses a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of more than 1500 and not more than 2500 and a vinyl acetate residue unit of 6 to 10% by weight, a compound represented by a specific formula of 100 to 3000 ppm and 2000 to 10000 ppm of alkyl sulfate are disclosed.

Further, in Patent Document 2, 0.00 of alkyl sulfate is added to 100 parts by weight of a vinyl chloride-vinyl acetate copolymer having a vinyl acetate residue unit of 5 to 15% by weight and an average degree of polymerization of 1500 to 2500. Vinyl chloride-vinyl acetate copolymer composition particles characterized by containing 5-2 parts by weight and 1-3 parts by weight of a higher alcohol and having an average particle size of 1-2 μm are disclosed.

JP 2016-188334 A JP 2017-105966 A

When a paste sol obtained from a vinyl chloride paste resin is used, for example, as an undercoat for automobiles, slip resistance (difficulty in slipping of the paste sol on the coating surface) is required. However, the conventional techniques as described above have room for improvement in terms of slip resistance.

An object of one aspect of the present invention is to realize a vinyl chloride-based paste resin that can provide a paste sol having excellent slip resistance.

In order to solve the above problems, the present inventors conducted intensive research and found that the slip resistance of the obtained paste sol was improved by using a relatively small amount of polymerization emulsifier in combination with the vinyl chloride polymer. The present inventors have found that it is possible to complete the present invention. The present invention includes the following aspects.
<1> Vinyl chloride containing a vinyl chloride polymer and a polymerization emulsifier, wherein the amount of the polymerization emulsifier is more than 0.30 parts by weight and 0.50 parts by weight or less per 100 parts by weight of the vinyl chloride polymer paste resin.
<2> The vinyl chloride paste resin according to <1>, wherein the vinyl chloride polymer is a copolymer of vinyl chloride and vinyl acetate.
<3> The vinyl chloride paste resin according to <1> or <2>, wherein the amount of the polymerization emulsifier is 0.40 to 0.50 parts by weight with respect to 100 parts by weight of the vinyl chloride polymer.
<4> The vinyl chloride paste resin according to any one of <1> to <3>, wherein the polymerization emulsifier contains sodium lauryl sulfate.
<5> The vinyl chloride paste resin according to <4>, wherein the amount of sodium lauryl sulfate in 100% by weight of the polymerized emulsifier is 85% by weight or more.
<6> A resin composition for automobile undercoat, containing the vinyl chloride paste resin according to any one of <1> to <5>.
<7> The automobile undercoat resin composition according to <6>, which is a sealant or an underbody coat.

According to one aspect of the present invention, it is possible to provide a vinyl chloride-based paste resin capable of obtaining a paste sol having excellent slip resistance.

It is a schematic diagram showing the slip-resistant evaluation method in an Example.

An embodiment of the invention will be described below, but the invention is not limited thereto. Unless otherwise specified in this specification, "A to B" representing a numerical range intends "A or more and B or less".

[1. Vinyl chloride paste resin]
A vinyl chloride paste resin according to one embodiment of the present invention contains a vinyl chloride polymer and a polymerization emulsifier, and the amount of the polymerization emulsifier is more than 0.30 parts by weight with respect to 100 parts by weight of the vinyl chloride polymer. It is 0.50 parts by weight or less.

For example, when a paste sol obtained from a vinyl chloride paste resin is used as an undercoat for automobiles, the paste sol is required to be difficult to slide off from the surface to be coated (coating surface). That is, it is required to improve the slip resistance of the paste sol. As a result of intensive studies by the present inventors, it has become clear that when the content of the polymerized emulsifier in the vinyl chloride paste resin is relatively small, the slip resistance of the resulting paste sol is improved. Usually, in the vinyl chloride paste resin, the amount of the polymerization emulsifier is about 0.6 to 1.5 parts by weight with respect to 100 parts by weight of the vinyl chloride polymer. For example, among the examples of Patent Document 1, the amount of the polymerization emulsifier in Example 4 (total amount of sodium lauryl sulfate and nonylpropenylphenol ethylene oxide 10 mol adduct sulfate ester ammonium salt) is the smallest, about 0.6 parts by weight. Met. Moreover, in Comparative Example 3 of Patent Document 2, it is disclosed that although about 0.3 parts by weight of a polymerized emulsifier was used, a paste sol could not be obtained. The relation between the amount of the polymerized emulsifier and the slip resistance is a new finding that has not been known so far. Based on this new knowledge, in one embodiment of the present invention, it is possible to provide a vinyl chloride paste resin with improved slip resistance by controlling the amount of the polymerized emulsifier.

As used herein, the term "vinyl chloride paste resin" means a resin containing a vinyl chloride polymer and used to prepare a paste sol. In the following, the vinyl chloride-based paste resin is also simply referred to as "paste resin".

In the present specification, "excellent slip resistance" means that when a paste sol prepared using the above paste resin is applied to a surface to be coated, the paste sol does not easily slide off on the surface. do. It can also be said that the paste sol is less likely to peel off or is less likely to be misaligned. The slip resistance can be evaluated by applying the paste sol to an electrodeposition coated plate, allowing it to stand still for a certain period of time, and then measuring the distance it slides down. A more specific method for evaluating the slip resistance will be described in Examples below.

<1-1. Vinyl chloride polymer>
As used herein, the term "vinyl chloride polymer" means a polymer containing at least structural units derived from vinyl chloride. The vinyl chloride-based polymer may be a vinyl chloride homopolymer, and is a copolymer containing a structural unit derived from a monomer copolymerizable with vinyl chloride in addition to a structural unit derived from vinyl chloride. There may be. In the present specification, vinyl chloride constituting the vinyl chloride polymer and monomers copolymerizable with vinyl chloride may be collectively referred to as "vinyl chloride monomer".

Examples of monomers copolymerizable with vinyl chloride include olefins such as ethylene, propylene and butene; vinyl esters of carboxylic acids such as vinyl acetate, vinyl propionate and vinyl stearate; methyl vinyl ether, ethyl vinyl ether and octyl. vinyl ethers having an alkyl group such as vinyl ether and lauryl vinyl ether; vinylidene halides such as vinylidene chloride; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride and itaconic anhydride and acid anhydrides thereof; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butyl benzyl maleate; aromatic vinyl compounds such as styrene, α-methylstyrene, and divinylbenzene unsaturated nitriles such as acrylonitrile; crosslinkable monomers such as diallyl phthalate; These may be used alone or in combination of two or more. The vinyl chloride-copolymerizable monomer is preferably used in an amount of 50% by weight or less in 100% by weight of the vinyl chloride-based monomer used for polymerization.

Among them, as the monomer copolymerizable with vinyl chloride, carboxylic acid vinyl esters, acrylic acid esters, methacrylic acid esters and the like are preferable, and carboxylic acid vinyl esters are more preferable. The vinyl chloride-based polymer is particularly preferably a copolymer of vinyl chloride and vinyl acetate. Thereby, it can be gelled at a low temperature. Hereinafter, a paste resin containing a copolymer of vinyl chloride and vinyl acetate is also referred to as a "vinyl chloride/vinyl acetate copolymer paste resin".

<1-2. Polymerization emulsifier>
As used herein, the term "polymerization emulsifier" means an emulsifier that can be used in polymerization for obtaining a vinyl chloride polymer from a vinyl chloride monomer.

In this specification, the amount of the polymerized emulsifier in the vinyl chloride paste resin is expressed as the number of parts of the polymerized emulsifier with respect to 100 parts by weight of the vinyl chloride polymer contained in the vinyl chloride paste resin. In the following, this is also simply referred to as "the amount of polymerized emulsifier".

A specific method for calculating the amount of the polymerized emulsifier will be described in Examples below. In addition, when multiple types of polymerization emulsifiers are contained in vinyl chloride paste resin, let the total amount of these multiple types be the amount of polymerization emulsifiers.

The amount of the polymerization emulsifier is more preferably more than 0.30 parts by weight and 0.50 parts by weight or less, more preferably 0.35 to 0.50 parts by weight, and 0.40 to 0.50 parts by weight. Part is particularly preferred. Thereby, the anti-slip property can be improved as described above while ensuring polymerization stability.

Polymerized emulsifiers include anionic emulsifiers and nonionic emulsifiers. An anionic emulsifier and a nonionic emulsifier may be used in combination.

Examples of anionic emulsifiers include carboxylic acids, alkylsulfonic acids, alkylbenzenesulfonic acids, α-olefinsulfonic acids, sulfosuccinic acids, alkylsulfosuccinic acids, alkyl sulfuric acids, polyoxyethylene alkyl ether sulfuric acids, polyoxyethylene alkylallyl ether sulfuric acids, alkyl phosphorus Salts of acids, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl allyl ether phosphates, and the like can be mentioned. Examples of the salt include potassium salt, sodium salt, ammonium salt and the like. These may be used alone or in combination of two or more. Among them, sodium alkylsulfate is preferable from the viewpoint of polymerization stability, defoaming property and fluidity of paste sol.

As the sodium alkylsulfate, sodium alkylsulfate having 8 to 20 carbon atoms is preferably used, and sodium alkylsulfate having an even number of carbon atoms or sodium alkylsulfate having an odd number of carbon atoms may be used. Examples of sodium alkylsulfate having an even number of carbon atoms include sodium octyl sulfate, sodium decylsulfate, sodium laurylsulfate, sodium myristylsulfate, sodium cetylsulfate, sodium stearylsulfate and sodium eicosylsulfate. Among these, sodium decyl sulfate, sodium lauryl sulfate, sodium myristyl sulfate, sodium cetyl sulfate, and sodium stearyl sulfate are particularly preferred. These may be used alone or in combination of two or more.

Among them, the polymerized emulsifier preferably contains sodium lauryl sulfate. Sodium lauryl sulfate is preferred from the viewpoint of easily ensuring polymerization stability. The amount of sodium lauryl sulfate in 100% by weight of the polymerized emulsifier is preferably 85% by weight or more, more preferably 90% by weight or more, and may be 100% by weight.

Nonionic emulsifiers include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether; Polyoxyalkylene alkylphenyl ethers such as oxyethylene polyoxypropylene alkylphenyl ether; Polyoxyalkylene block copolymers such as polyoxyethylene polyoxypropylene block copolymers and polyoxyethylene polyoxypropylene polyoxyethylene block copolymers; Glycerin fatty acid esters , sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene fatty acid esters; silicone emulsifiers and the like.

<1-3. Other Ingredients>
The vinyl chloride-based paste resin may contain a dispersing aid, an oil-soluble initiator, a water-soluble initiator, etc. in addition to the vinyl chloride-based polymer and polymerization emulsifier described above.

Examples of dispersion aids include higher alcohols and higher fatty acids. Higher alcohols include hexyl alcohol (6 carbon atoms), heptyl alcohol (7 carbon atoms), octyl alcohol (8 carbon atoms), nonyl alcohol (9 carbon atoms), decyl alcohol (10 carbon atoms), undecyl alcohol (10 carbon atoms), 11), lauryl alcohol (dodecyl alcohol, 12 carbon atoms), tridecyl alcohol (13 carbon atoms), myristyl alcohol (14 carbon atoms), pentadecyl alcohol (15 carbon atoms), cetyl alcohol (16 carbon atoms), hepta Decyl alcohol (17 carbon atoms), stearyl alcohol (18 carbon atoms), nonadecyl alcohol (19 carbon atoms), eicosyl alcohol (20 carbon atoms) and the like can be mentioned. Higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid and the like. These may be used alone or in combination of two or more. The amount of the dispersion aid used may be 0 to 5 parts by weight, or 0.3 to 2 parts by weight, per 100 parts by weight of the vinyl chloride monomer.

Examples of oil-soluble initiators include organic peroxide initiators and azo initiators. Examples of organic peroxide-based initiators include diacyl peroxides such as dilauroyl peroxide and di-3,5,5-trimethylhexanoyl peroxide; Examples include peroxydicarbonates, peroxyesters such as t-butyl peroxypivalate, t-butyl peroxyneodecanoate and cumyl peroxyneodecanoate. Azo initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4- dimethylvaleronitrile) and the like. These may be used alone or in combination of two or more. The amount of the oil-soluble initiator used may be 0 to 3 parts by weight per 100 parts by weight of the vinyl chloride monomer.

Water-soluble initiators include ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide and the like. If necessary, a reducing agent such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate (Rongalite), ascorbic acid, sodium ascorbate, etc. is used in combination. These may be used alone or in combination of two or more. The water-soluble initiator may be used in an amount of 0 to 3 parts by weight per 100 parts by weight of the vinyl chloride monomer.

[2. Method for producing vinyl chloride paste resin]
A method for producing a vinyl chloride-based paste resin according to an embodiment of the present invention may include a polymerization step of polymerizing a vinyl chloride-based monomer in the presence of a polymerization emulsifier. The polymerized emulsifier is added so that the amount of the polymerized emulsifier per 100 parts by weight of the vinyl chloride polymer in the obtained vinyl chloride paste resin is more than 0.30 parts by weight and not more than 0.50 parts by weight. For example, the amount of the polymerization emulsifier added to 100 parts by weight of the vinyl chloride monomer is preferably more than 0.30 parts by weight and 0.45 parts by weight or less, and more than 0.30 parts by weight and 0.40 parts by weight or less. It is more preferable to have

The polymerization method is not particularly limited, and examples thereof include a fine suspension polymerization method, an emulsion polymerization method, a seed emulsion polymerization method and the like. In the fine suspension polymerization method, a vinyl chloride monomer, a polymerization emulsifier, a dispersing aid, an oil-soluble initiator and the like are added to an aqueous medium to carry out polymerization. In the emulsion polymerization method, a vinyl chloride monomer, a polymerization emulsifier, a dispersing aid, a water-soluble initiator and the like are added to an aqueous medium to carry out polymerization. In the seed emulsion polymerization method, particles (seeds) obtained by the emulsion polymerization method are used. A vinyl chloride paste resin latex (aqueous homogenous dispersion) is obtained by these methods.

The production method may include a drying step of drying the latex obtained by the polymerization step. By drying the latex by spray drying or the like, a vinyl chloride paste resin can be obtained. Before drying, the vinyl chloride paste resin latex may be passed through a sieve to remove coarse particles, if necessary. Alternatively, the latex obtained from each polymerization may be mixed and the resulting mixture may be spray-dried. If necessary, the spray-dried vinyl chloride paste resin may be pulverized.

[3. Automobile undercoat resin composition]
A resin composition for automobile undercoat according to one embodiment of the present invention contains the vinyl chloride-based paste resin described above. Automotive primer resin compositions include, for example, sealants and underbody coats. It should be noted that an embodiment of the present invention may also include resin compositions for applications other than automotive primers. Examples of such uses include wallpaper, floor material cushion floor, floor material carpet tile, ceiling material, leather, canvas, steel plate, automobile interior material, marking film, table cloth, toys, dolls, gloves, waterproof coating materials, Examples include insulating coating materials, medical supplies, cap seals, and food models. Hereinafter, these resin compositions are collectively referred to simply as "resin compositions".

The resin composition contains a plasticizer in addition to the vinyl chloride paste resin. The resin composition contains a vinyl chloride paste resin and a plasticizer, and if necessary, a stabilizer, a diluent, a viscosity reducing agent, a filler, an adhesion imparting agent, an antioxidant, a reinforcing agent, an ultraviolet absorber, It can be obtained by adding a foaming agent, a flame retardant, an antistatic agent, a lubricant, a pigment, a surface treatment agent, a thixotropic agent, an antifungal agent, a detergent, etc., and stirring and mixing. The resin composition may be a paste sol. Further, the resin composition can be molded by heat gelation.

Plasticizers include di-2-ethylhexyl phthalate (DOP), di-normal octyl phthalate, dibutyl phthalate, diisononyl phthalate (DINP), phthalate plasticizers such as butyl benzyl phthalate; tricresyl phosphate, tri-2- Phosphate plasticizers such as ethylhexyl phosphate; Adipate plasticizers such as di-2-ethylhexyl adipate; Sebacate plasticizers such as di-2-ethylhexyl sebacate; Di-2-ethylhexyl azelate, etc. azelaic acid ester plasticizers; trimellitic acid ester plasticizers such as tri-2-ethylhexyl trimellitate; polyester plasticizers; di-2-ethylhexyl benzoate, diethylene glycol dibenzoate, 2,2,4-trimethyl- Benzoic acid ester plasticizers such as 1,3-pentanediol isobutyrate benzoate; citric acid ester plasticizers such as acetyltributyl citrate; glycolic acid ester plasticizers; chlorinated paraffin plasticizers; chlorinated fatty acid esters plasticizer; epoxy plasticizer; texanol isobutyrate; These may be used alone or in combination of two or more. Among them, phthalate plasticizers are preferred, and di-2-ethylhexyl phthalate and diisononyl phthalate are more preferred. The plasticizer may be used in an amount of 30 to 200 parts by weight, 40 to 150 parts by weight, or 50 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride paste resin.

Stabilizers include organic tin stabilizers such as dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin malate, dioctyltin malate, dibutyltin laurate; lead stearate, dibasic lead phosphite, tribasic lead-based stabilizers such as lead sulfate; calcium-zinc-based stabilizers, barium-zinc-based stabilizers; epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene; These may be used alone or in combination of two or more. The stabilizer may be used in an amount of 0 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride paste resin.

The diluent is not particularly limited, and includes, for example, 2,2,4-trimethyl-1,3-pentadiol diisobutyrate (TXIB), normal paraffin, isoparaffin and the like. These may be used alone or in combination of two or more. The diluent may be used in an amount of 0 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride paste resin.

The filler is not particularly limited, and examples thereof include general ground calcium carbonate, colloidal silica, synthetic calcium carbonate, and the like. These may be used alone or in combination of two or more. The filler may be used in an amount of 0 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride paste resin.

The adhesion imparting agent is not particularly limited, and examples thereof include polyamide resins and polyethyleneimine resins. These may be used alone or in combination of two or more. The filler may be used in an amount of 0 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride paste resin.

The present invention is not limited to the above-described embodiments, but can be modified in various ways within the scope of the claims, and can be obtained by appropriately combining technical means disclosed in different embodiments. is also included in the technical scope of the present invention.

The present invention will be described in detail based on examples, but the present invention is not limited to these.

〔Evaluation method〕
Each evaluation method used in the examples is shown below.

(1) Confirmation of Polymerization Stability Polymerization stability was confirmed by checking whether or not a latex was obtained at the time when the polymerization described below was completed. When the latex was obtained, it was evaluated as “◯ (good)”, and when it was not obtained, it was evaluated as “× (poor)”.

(2) Calculation of amount of polymerized emulsifier in paste resin The amount of polymerized emulsifier in paste resin (amount of polymerized emulsifier per 100 parts by weight of vinyl chloride polymer) was calculated as follows.

First, 2 g of the latex obtained by polymerization was placed in an aluminum dish, dried in an oven at 180° C. for 30 minutes, and the solid content weight after drying was measured. The solid content concentration was calculated by the following formula (I) from the solid content weight after drying and the latex weight before drying.
Solid content concentration [%] = 100 x solid content weight after drying [g] / latex weight before drying [g] (I)
From the above solid content concentration, the amount of monomers consumed during polymerization was calculated by the following formula (II), and this was taken as the polymerization conversion rate.
Polymerization conversion rate [%] = {solid content concentration [%] / (100 - solid content concentration [%])} x {water [parts by weight] / (vinyl chloride monomer [parts by weight] + vinyl acetate monomer [parts by weight])}×100 (II)
Assuming that the entire amount of the charged emulsifier was incorporated into the vinyl chloride paste resin when the latex was dried, the number of charged parts of the emulsifier was divided by the polymerization conversion rate to obtain 100 parts by weight of the vinyl chloride polymer. was calculated. That is, the amount of the polymerized emulsifier was determined by the following formula (III).
Amount of polymerization emulsifier [parts by weight] = 100 × number of parts charged of polymerization emulsifier [parts by weight] / polymerization conversion rate [%] (III)
(3) Slip resistance evaluation method of paste sol (3-1) Preparation of paste sol 100 parts by weight of the dried paste resin and 67 parts by weight of diisononyl phthalate (DINP) are added to a 500 mL SUS cup and homogenized. mixed to After that, 50 parts by weight of general heavy calcium carbonate (BF300, manufactured by Bihoku Funka Kogyo Co., Ltd.), 67 parts by weight of colloidal calcium (Shiraishi Calcium Co., Ltd., Hakuenka CCR), and 13 parts by weight of DINP were added to the SUS cup. Add and mix again until uniform. The resulting mixture was kneaded at room temperature at 1000 rpm for 1 minute using a dissolver kneader (manufactured by ROBO MICS/TOKUSHU KITA, dissolver blade diameter 5 cm).

After kneading, 3.4 parts by weight of a polyamide resin (VERSAMID (registered trademark) 140, manufactured by GABRIEL) and 13 parts by weight of a hydrocarbon-based detergent (Shellsol S, manufactured by Japan Chemtech Co., Ltd.) were added. Mix until uniform. The resulting mixture was kneaded for 1 minute at 1000 rpm at room temperature using the dissolver type kneader. The resulting mixture was transferred to an Ishikawa type kneader (manufactured by Ishikawa Kogyo Co., Ltd.), 20 parts by weight of DINP was added, and the mixture was mixed until uniform. After that, a paste sol was produced by subjecting the obtained mixture to a defoaming treatment.

(3-2) Slip Resistance Evaluation Method FIG. 1 is a schematic diagram showing a slip resistance evaluation method. Denatured alcohol (Etacol 7, manufactured by Sankyo Chemical Co., Ltd.) was applied to the surface of an electrodeposition coated plate 1 (manufactured by Miki Coating Co., Ltd., length (long side) 140 mm x width (short side) 25 mm x thickness 0.8 mm). did. A degreasing treatment was performed by wiping off the denatured alcohol with a cloth.

Using a semicircular coater, a paste sol 2 (which was allowed to stand at room temperature of 25° C. and humidity of 50% for one day) was applied to a degreased electrodeposition coated plate 1 in a semicylindrical shape (vertical ( Long side) 100 mm, width (short side) 12 mm, height 6 mm). That is, the applied paste sol 2 has a semicircular shape in the height direction.

The electrodeposition coated plate 1 coated with the paste sol 2 was hung so that the short side was horizontal and the long side was vertical, and left to stand still for 30 minutes. FIG. 1 shows a state 1000 in which the electrodeposition coated plate 1 is suspended and a state 1001 viewed from the short side. After 30 minutes had elapsed, the distance Z that the paste sol 2 slipped from the original position 10 of application was measured. The shorter the slipped distance Z, the better the slip resistance. When the distance Z that the paste sol 2 slipped down was 7 mm or more, it was judged as "x (not good)", and when it was less than 7 mm, it was judged as "good (good)".

[Example 1]
80 parts by weight of water (ion-exchanged water), 0.40 parts by weight of sodium lauryl sulfate (polymerization emulsifier), 0.40 parts by weight of cetyl alcohol, 0.40 parts by weight of cetyl alcohol, and 0.40 parts by weight of stearyl alcohol shown in Table 1 were placed in a stainless steel pressure vessel equipped with a stirrer. 43 parts by weight, 0.05 parts by weight of cumyl peroxyneodecanoate, and 0.03 parts by weight of t-butyl peroxyneodecanoate were charged and degassed. Thereafter, 6.5 parts by weight of vinyl acetate monomer and 93.5 parts by weight of vinyl chloride monomer were charged into the above pressure vessel and homogenized. After that, the temperature inside the pressure vessel was raised to 43.5° C. to carry out polymerization. When the polymerization pressure dropped, the unreacted monomer was removed to terminate the polymerization. The latex from which coarse particles were removed was spray-dried using a spray dryer (Mitsubishi Kakoki Co., Ltd.) under conditions of an inlet temperature of 105°C and an outlet temperature of 50°C. Thus, a vinyl chloride/vinyl acetate copolymer paste resin was obtained.

Since the polymerization conversion rate of the obtained paste resin was 80.8%, the amount of the polymerization emulsifier was 0.50 parts by weight with respect to 100 parts by weight of the vinyl chloride polymer.

[Example 2]
A vinyl chloride/vinyl acetate copolymer paste resin was obtained in the same manner as in Example 1, except that the amount of sodium lauryl sulfate, which is a polymerization emulsifier, was changed to 0.35 parts by weight. Since the polymerization conversion rate of the obtained paste resin was 85.7%, the amount of the polymerization emulsifier to 100 parts by weight of the vinyl chloride polymer was 0.41 parts by weight.

[Comparative Example 1]
A vinyl chloride/vinyl acetate copolymer paste resin was obtained in the same manner as in Example 1, except that the amount of sodium lauryl sulfate, which is a polymerization emulsifier, was changed to 0.48 parts by weight. Since the polymerization conversion rate of the obtained paste resin was 90.1%, the amount of the polymerization emulsifier to 100 parts by weight of the vinyl chloride polymer was 0.53 parts by weight.

[Comparative Example 2]
The same operation as in Example 1 was performed except that the amount of sodium lauryl sulfate, which is a polymerization emulsifier, was changed to 0.25 parts by weight, but no paste resin was obtained.

〔Evaluation results〕
Table 1 shows the raw materials, polymerization temperatures, polymerization conversion rates, evaluation results, etc. of the paste resins obtained in Examples and Comparative Examples.

In Examples 1 and 2 and Comparative Example 1, stable latexes were obtained. However, Examples 1 and 2 in which the amount of the polymerization emulsifier is 0.50 parts by weight or less with respect to 100 parts by weight of the vinyl chloride polymer are compared to Comparative Example 1 in which the amount of the polymerization emulsifier exceeds 0.50 parts by weight. Excellent slip resistance. In addition, in Comparative Example 2 in which the added amount of the polymerization emulsifier was 0.25 parts by weight, the paste resin could not be obtained as described above.

One aspect of the present invention can be suitably used in applications where the paste sol is required to have slip resistance.

1 electrodeposition coated plate 2 paste sol

Claims (7)

containing a vinyl chloride polymer and a polymerization emulsifier,
A vinyl chloride-based paste resin, wherein the amount of the polymerization emulsifier is more than 0.30 parts by weight and not more than 0.50 parts by weight with respect to 100 parts by weight of the vinyl chloride-based polymer. 2. The vinyl chloride paste resin according to claim 1, wherein the vinyl chloride polymer is a copolymer of vinyl chloride and vinyl acetate. 3. The vinyl chloride paste resin according to claim 1, wherein the amount of said polymerization emulsifier is 0.40 to 0.50 parts by weight with respect to 100 parts by weight of said vinyl chloride polymer. The vinyl chloride paste resin according to any one of claims 1 to 3, wherein the polymerization emulsifier contains sodium lauryl sulfate. 5. The vinyl chloride paste resin according to claim 4, wherein the amount of sodium lauryl sulfate in 100% by weight of the polymerized emulsifier is 85% by weight or more. A resin composition for automobile undercoat, comprising the vinyl chloride paste resin according to any one of claims 1 to 5. 7. The automotive undercoat resin composition according to claim 6, which is a sealant or an underbody coat.

Images