JP2009167229A - Plastisol and textile ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plastisol having low viscosity and excellent heat resistance and storage stability, suitable for textile ink, and reducing a load on the environment with a less amount of generated VOC (volatile organic compounds) when processing, and to provide the textile ink having excellent storage stability, and, in a coated film formed on a textile, having good balance of strength and elasticity and inhibiting tucking. <P>SOLUTION: The plastisol contains polymer particles and a trimethylolpropane ester represented by formula (1). The content of the trimethylolpropane ester is ≥20 mass% and ≤80 mass%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a plastisol excellent in storage stability and heat resistance, and a textile ink obtained by using the plastisol, and more specifically, in a coating film formed using a textile ink with less burden on the environment, strength and elasticity. The present invention relates to a textile ink having excellent flexibility and suppressing tack (stickiness).

  Pasty materials in which fine particles of thermoplastic polymer are dispersed in a plasticizer are collectively referred to as plastisol. In particular, plastisol using a vinyl chloride polymer has been widely used for various years as a vinyl chloride sol in various industrial fields. Yes. However, since vinyl chloride sols cause environmental problems such as dioxins when incinerated at low temperatures, acrylic plastisols using acrylic polymer fine particles have been proposed in order to reduce the environmental burden (patent document) 1)), and its practical use is progressing.

  In recent years, phthalate-based compounds used as plasticizers are also volatile, so in order to further reduce the environmental impact, their use has been discontinued in some fields and non-phthalate There is a movement to use acid ester plasticizers. Various types of non-phthalate plasticizers have been put into practical use and have been proposed. Examples thereof include benzoate compounds, citrate compounds, and polyester compounds.

  However, these plasticizers do not extend to phthalate ester plasticizers in terms of physical properties such as heat resistance and viscosity, and cost. It has not yet replaced ester plasticizers.

  In particular, regarding acrylic plastisols, there is a demand for the development of plasticizers that are practically satisfactory in terms of gelation performance, storage stability, viscosity, etc., by optimizing compatibility and wettability with acrylic polymers. Specifically, an acrylic plastisol obtained by combining an acrylic polymer and a benzoate plasticizer has been proposed (Patent Document 2, etc.). However, since the benzoate ester plasticizer has a polyether skeleton, the heat resistance is extremely low, and the plastisol using this is insufficient in terms of heat resistance. When the heat resistance is insufficient, there are various problems such as volatilization of a volatile organic compound (VOC) during plastisol processing and odor remaining in a molded product.

  In addition, liquid polyester compounds and acrylic compounds have been proposed as non-phthalate ester plasticizers (Patent Document 3, etc.). These plasticizers are commercially available and have a mass average molecular weight of 1000 or more, and have a very high viscosity as a plasticizer. For this reason, the obtained plastisol also has a problem that it has a high viscosity and cannot be easily used industrially. In addition, when a large amount of diluent is used in combination to reduce the viscosity, a diluent gas is generated, which conflicts with the solution of the volatile organic compound (VOC) problem.

  It has also been reported that trimethylolpropane ester is used as a plasticizer for polyvinyl chloride resin (Patent Document 4). By using the plasticizer, it is made of polyvinyl chloride resin that has high tensile strength and elongation, prevents the plasticizer from exuding to the surface (migration resistance), and reduces the weight loss during heating of the sheet. Although a molded sheet is obtained, a plastisol to which trimethylolpropane ester is applied is not known.

By the way, textile inks are used to print designs and the like on various textiles and to form coating films having various functions. Textile ink contains plastisol as a coating film-forming component and functional components such as pigments. The coating film formed on the textile using this ink has strength, flexibility and flexibility to follow the deformation of the textile. It is required to have sex. However, strength and moderate stretchability are contradictory properties, and there is a need for a plastisol for textile ink that can form a better coating film having both strength and stretchability. Furthermore, there is a demand for the coating film on the textile not having tack (stickiness), and there is a demand for a plastisol that can satisfy the strength and stretchability and can form a coating film with reduced tack. Furthermore, the flexibility of the resulting coating film and the storage stability of the plastisol contained in the textile ink are contradictory properties, and there is a demand for a textile ink that satisfies these characteristics. Acrylic plastisols tend to lack storage stability, such as the sol state changing during storage. For textile inks using acrylic plastisols, adjustment of the flexibility of the resulting coating film and the storage stability of the textile ink Extremely difficult.
International Publication No. WO00 / 01748 Japanese Patent Laid-Open No. 11-124483 JP 2001-247739 Special table 2004-517184

  An object of the present invention is to provide a plastisol that has a low viscosity, is excellent in heat resistance and storage stability, is suitable for textile inks, has a small amount of VOC generated during processing, and can reduce the burden on the environment. It is in. Another object of the present invention is to provide a textile ink that is excellent in storage stability, has a good balance between strength and stretchability in a coating film formed on the textile, and suppresses tack.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that plastisol containing polymer fine particles and trimethylolpropane ester plasticizer is extremely excellent in storage stability and is formed on a textile using this. It was found that the coated film was excellent in both strength and stretchability and suppressed tack, and the present invention was completed.

  That is, the present invention relates to a plastisol containing polymer particles and a trimethylolpropane ester represented by the formula (1), wherein the content of the trimethylolpropane ester is 20% by mass or more and 80% by mass or less.

(In the formula, R ₁ to R ₃ independently represent a hydrocarbon group.)
The present invention also relates to a textile ink characterized by using the plastisol.

  The plastisol of the present invention has a low viscosity, is excellent in heat resistance and storage stability, is suitable for textile inks, has a small amount of processing, particularly VOC, and can reduce the burden on the environment. In addition, the textile ink of the present invention is excellent in storage stability, has a good balance between strength and stretchability in a coating film formed on the textile, and can suppress tack.

  The plastisol of the present invention contains polymer particles and a trimethylolpropane ester represented by the formula (1), and the content of the trimethylolpropane ester is 20% by mass or more and 80% by mass or less. And

  The polymer particles contained in the plastisol of the present invention are not particularly limited as long as they are compatible with the trimethylolpropane ester represented by the formula (1), and are polyvinyl chloride polymers and acrylic polymers. And particles such as polystyrene-based polymers. Among these, in particular, the acrylic polymer particles have a low environmental load, such as a small amount of harmful gas emission during incineration, and are compatible with the trimethylolpropane ester represented by the formula (1). Is preferable.

  The acrylic polymer is preferably an industrially available (meth) acrylic acid ester polymer. Specific examples of the (meth) acrylic acid ester polymer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meta ) (Meth) acrylates of linear alkyl alcohols such as acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate; (meth) of cyclic alkyl alcohols such as cyclohexyl (meth) acrylate Examples include polymers containing acrylates as monomers. Among these, polymers having methyl acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate as monomers are these. A monomer can be easily obtained and is preferable from the viewpoint of industrial practical use. The (meth) acrylic acid ester polymer may be a copolymer in which these monomers are appropriately combined. Here, (meth) acrylate is a general term for acrylate and methacrylate.

  Furthermore, the (meth) acrylic acid ester polymer may be a copolymer of the monomer of the (meth) acrylic acid ester and a copolymerizable monomer. As the monomer copolymerizable with the monomer of the (meth) acrylic acid ester, methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-succinoloyloxyethyl methacrylate, Carboxyl group-containing unsaturated monomers such as 2-malenoyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate; sulfonate group-containing unsaturated compounds such as allyl sulfonic acid Monomer; Phosphoric acid group-containing (meth) acrylate such as 2- (meth) acryloyloxyethyl acid phosphate; Carbonyl group-containing (meth) acrylate such as acetoacetoxyethyl (meth) acrylate; 2-hydroxyethyl ( Meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. Roxyl group-containing (meth) acrylate; Epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate; Amino group-containing (meth) acrylate such as N-dimethylaminoethyl (meth) acrylate and N-diethylaminoethyl (meth) acrylate Acrylamide and its derivatives such as acrylamide, diacetone acrylamide, N-methylol acrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl acrylamide; urethane-modified acrylate; epoxy-modified acrylate; silicone-modified acrylate; ) Edylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, Polyfunctional monomers such as trimethylolpropane (meth) acrylates, and glycidyl (meth) an epoxy group-containing compound such as acrylate.

  The (meth) acrylic acid ester polymer is preferably a compound containing 50% by mass or more of the (meth) acrylic acid ester unit.

  The acrylic polymer preferably has a weight average molecular weight (Mw) of 500,000 to 3,000,000. If the molecular weight of the acrylic polymer is 500,000 or more, the textile ink using the acrylic polymer has excellent storage stability and can form a coating film having an appropriate strength. It is possible to suppress the plastisol from becoming a high viscosity.

  The polymer particles may have a uniform composition throughout the particle structure, but preferably have a multilayer structure. As a multilayer structure, a core-shell structure having a core layer and a shell layer having different compositions on the seed particle, a structure of three or more layers including a plurality of shell layers, and the composition continuously changes from the center to the surface. Examples thereof have a gradient type structure.

  When the polymer particles are acrylic polymer particles, those having a multilayer structure are preferable. Preferably, the core layer is formed of an acrylic polymer component that is compatible with the plasticizer, and the surface shell layer is formed of an acrylic polymer component that is incompatible with the plasticizer. By having such a multilayer structure, the core layer is covered with the surface layer, the contact with the plasticizer is suppressed, the gelation of the acrylic polymer particles in the plastisol is suppressed, and the plastisol and the same are used. Ink storage stability is improved. Furthermore, it is possible to easily adjust the strength and stretchability of the coating film obtained using this.

  The acrylic polymer particles include secondary particles such as primary particles containing the acrylic polymer, particles in which the primary particles are aggregated with a weak cohesive force, particles aggregated with a strong cohesive force, and particles fused to each other by heat. The particles may be particles having a higher-order structure by processing such as granulation of these secondary particles. Higher-order structure of acrylic polymer particles is to improve physical properties such as suppression of powdering of acrylic polymer particles and improvement of fluidity, and physical properties such as suppression of gelation to plasticizer in plastisol. It can be performed according to usage and requirements, such as the purpose of improvement.

  In the production of the polymer particles having the above multi-layer structure, a monomer is polymerized at a critical micelle concentration or less to form seed particles, and then at least one of an initiator and a chain transfer agent is added in the presence of the seed particles. Thus, the step of polymerizing the monomer may be performed twice or more.

  In the step of forming the seed particles, in addition to the (meth) acrylates such as methyl methacrylate, if necessary, a monomer having a functional group such as an acid group is dispersed in a dispersion medium at a concentration equal to or lower than the critical micelle concentration. If necessary, a polymerization initiator or the like is added and polymerized to obtain seed particles. By polymerizing at a concentration equal to or lower than the critical micelle concentration, seed particles having a relatively large particle size can be obtained. Examples of the dispersion medium to be used include water. The polymerization initiator used is potassium persulfate, ammonium persulfate, persulfate of sodium persulfate; organic peroxides of benzoyl peroxide and t-butyl hydroperoxide; redox polymerization by a combination of an oxidizing agent and a reducing agent. An initiator etc. can be mentioned.

  In the presence of the obtained seed particles, a monomer that forms a core is added to perform a polymerization reaction, and then a monomer that forms a shell is added and the polymerization reaction is sequentially repeated, so that a multilayer is formed. Structured particles can be formed. As the monomer for forming the core and shell, in addition to the above (meth) acrylate, a crosslinkable monomer can be used together with an initiator, a chain transfer agent and the like. These monomers can be used in different compositions when performing a plurality of polymerization steps. In addition, as a method of adding the initiator and the chain transfer agent, a method of adding the initiator and the chain transfer agent as they are, or as an aqueous solution or a dispersion medium at one time before or during the polymerization of the monomer, or a plurality of methods Any of a method of charging in divided times, a method of dropping, or the like may be used.

  After the completion of such a polymerization step, the polymer can be recovered from the dispersion medium by a method such as a spray drying method (spray drying method) or a coagulation method. Among these recovery methods, a large number of primary particles aggregate to create a state in which primary particles are not firmly bonded to each other in agglomerated particles (secondary particles or higher-order structures) and are loosely aggregated. From the viewpoint of improving dispersibility, a recovery method by a spray drying method that is easy to perform is preferable.

  The average particle diameter of the primary particles of the polymer particles is preferably 300 nm or more, and more preferably 500 nm or more. If the average particle diameter of the primary particles is 300 nm or more, the storage stability tends to be good in plastisol.

  Here, the average particle diameter refers to the volume average primary particle diameter and the number primary particle diameter in an aqueous dispersion of polymer particles prepared so that the transmittance is in the range of 75 to 95%. A value measured using a particle size distribution measuring apparatus (LA-920 manufactured by Horiba, Ltd.) can be used.

  The content of the polymer particles in the plastisol is preferably 20% by mass or more and 80% by mass or less. If the content of the polymer particles is 20% by mass or more, a textile ink capable of forming a coating film having strength can be provided, and if it is 80% by mass or less, the coating film having excellent stretchability can be formed. Possible textile inks can be given.

  The trimethylolpropane ester contained in the plastisol of the present invention is represented by the formula (1).

In the formula, R ₁ , R ₂ and R ₃ independently represent a hydrocarbon group. The hydrocarbon group represented by R ₁ , R ₂ , or R ₃ is preferably selected from a phenyl group or an alkyl group, and the alkyl group preferably has 3 to 10 carbon atoms, particularly with an acrylic polymer. Excellent compatibility, low viscosity, excellent heat resistance, reduce the amount of VOC generated during processing, reduce the burden on the environment, excellent storage stability, and suppress odor of molded products A plastisol can be provided.

  Further, trimethylolpropane ester (TMP) represented by the formula (1) is specifically trimethylolpropane tri-2-ethyl hexanoate (triethylpropylene-tri- (2-ethyl hexanoate)), benzoic acid 2,2-bis (2-ethylhexanoyloxymethyl) butyl ester (benzoic acid 2,2-bis- (2-ethyl-hexyloxymethyl) -butyl ester), ethyl 2-hexanoate 2,2-bis (benzoyloxymethyl) ) Butyl ester (2-ethylhexanoic acid 2,2-bis- (benzoyloxymethyl) -butyl ester), trimethylol propylene Tri benzoate (trimethylolpropane-tri-benzoate), and the like. The trimethylolpropane ester represented by the formula (1) is preferably a mixture of two or more of the above-exemplified examples, and more preferably a mixture of four or more. By using it as a mixture, the physical property balance can be made better, and the migration resistance for suppressing the exudation of the plasticizer from the surface of the molded article is excellent.

  When the trimethylolpropane ester represented by the formula (1) is used as a mixture, the amount of ethyl trimethylolpropane tri-2-hexanoate is 5% by mass or more and 60% by mass or less, and 2,2-bis (2-ethylhexanoyloxy) benzoate. Methyl) butyl ester is 20% by mass to 70% by mass, ethyl 2-hexanoate 2,2bis (benzoyloxymethyl) butyl ester is 5% by mass to 50% by mass, and trimethylolpropane tribenzoate is 1% by mass. % To 30% by mass, more preferably 15% to 40% by mass of trimethylolpropane tri-2-hexanoate, 2,2-bis (2-ethylhexanoyloxymethyl) butyl benzoate 40 mass% or more and 50 mass% or less of ester, 2-hexanoic acid ethyl 2,2 bis Zoyloxymethyl) butyl ester is 15% by mass to 35% by mass, and trimethylolpropane tribenzoate is 1% by mass to 10% by mass (the total amount of all the compounds is 100% by mass). It is.

  The mixture of trimethylolpropane ester can be produced by using trimethylolpropane as an aliphatic acid ethyl 2-hexanoate and aromatic acid benzoic acid as raw materials, but as a trimethylolpropane ester mixture “BET” (LG Chemical Co., Ltd.) can be applied.

  The content of the trimethylolpropane ester in the plastisol is 20% by mass or more and 80% by mass or less. Here, the content ratio of the trimethylolpropane ester is a ratio with respect to the total mass of the polymer particles and the trimethylolpropane ester represented by the formula (1). If the content ratio of the trimethyl propane ester is 20% by mass or more, the resulting coating film has flexibility, and if it is 80% by mass or less, bleeding out is suppressed in the coating film. The content ratio of the trimethylolpropane ester is more preferably 35% by mass or more.

  The plastisol of the present invention can contain other plasticizers as necessary within the range not inhibiting the function of trimethylolpropane ester. Specific examples of other plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, and butyl benzyl phthalate. Phthalate ester plasticizers; dimethyl adipate, dibutyl adipate, diisobutyl adipate, dihexyl adipate, di-2-ethylhexyl adipate, diisononyl adipate, dibutyl diglycol adipate and the like adipate ester plasticizers; trimethyl phosphate, triethyl phosphate, tributyl phosphate, Tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate Phosphate ester plasticizers such as phosphate, trixylenyl phosphate, cresylphenyl phosphate; Trimellitic ester plasticizers such as tri-2-ethylhexyl trimellitate; Dimethyl sebacate, dibutyl sebacate, di-2- Sebacic acid ester plasticizers such as ethylhexyl sebacate; Aliphatic polyester plasticizers such as poly-1,3-butanediol adipate; Epoxidized ester plasticizers such as epoxidized soybean oil; Alkylsulfonic acid phenyl esters Alkyl sulfonic acid phenyl ester plasticizer; Alicyclic dibasic acid ester plasticizer; Polypropylene plasticizer such as polypropylene glycol and polybutylene glycol; Citric acid esters such as acetyltriethyl citrate and acetyltributyl citrate Raise Door can be. These plasticizers can be used alone or in combination of two or more.

  These plasticizers are preferably used in a range of 100 parts by mass or less with respect to 100 parts by mass of the trimethylolpropane ester.

  The plastisol of the present invention may contain various additives to be added to the textile ink described later as long as the functions of the polymer particles and the trimethylolpropane ester are not inhibited.

  Examples of the method for producing the plastisol include a method in which polymer particles and a plasticizer are mixed and stirred at a predetermined ratio.

  The textile ink of the present invention uses the above plastisol. The textile ink of the present invention contains a functional component together with the above plastisol, and can form a coating film imparted with functionality such as colorability, concealability, weight reduction and design. Examples of such functional components include natural inorganic pigments such as clay, barite, mica, and ocher, and synthetic inorganic inorganic materials such as titanium oxide, zinc yellow, barium sulfate, zinc oxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, and carbon black. Pigments, metal powders such as aluminum powder and zinc powder, natural dye-based pigments such as muder lake, nitroso-based, azo-based, phthalocyanine-based, basic dye-based, organic fluorescent-based pigments such as synthetic organic pigments, mineral fillers And fillers such as synthetic fillers or vegetable fillers. Examples of the filler include fiber glass, wood powder, fly ash, cellulose fiber, rice husk, nut shell, hollow sphere, plastic sphere, fumed silica, and glass sphere. In order to improve the concealability, it is preferable to contain titanium oxide.

  The content ratio of the functional component is preferably 0.01 parts by mass or more and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polymer particles in order to obtain effects such as coloring. . Moreover, in order to obtain favorable coating-film strength, it is preferable that it is 400 mass parts or less with respect to 100 mass parts of polymer particles, and it is more preferable that it is 300 mass parts or less.

  The textile ink is an antioxidant, a non-halogen flame retardant, a viscosity modifier, a diluent, an antifoaming agent, an antifungal agent, an antibacterial agent, and a surfactant as long as the functions of the plastisol and functional components are not impaired. Additives such as lubricants, ultraviolet absorbers, fragrances, leveling agents, and adhesives can be blended.

  The textile ink can be prepared by a method of mixing and stirring the polymer particles, plasticizer, functional component and, if necessary, the additive, such as a dissolver, kneader, planetary mixer, three roll mill, etc. A stirrer can be used.

  Textiles that form a coating film using the textile ink may be any of fabrics such as woven fabrics and knitted fabrics, felts, and nonwoven fabrics. Specifically, shirts, trainers, aprons, socks, gloves and other clothing, shoes, bags and other miscellaneous goods, curtains, tablecloths, tapestries and other interior decorations, chairs, sofas and other furniture, vehicle seats, and headrests , Tonneau covers, sun visors, and other canvases.

  As a method for forming a coating film on these textiles, direct printing such as screen printing, thermal transfer printing, or the like can be applied. Thermal transfer printing is a method of forming a coating film by applying a textile ink composition onto a release paper or the like and then heat-pressing the gelled film obtained by heating to the textile. The coating film formed on the textile is solidified by heating. The heating conditions can be appropriately selected depending on the thickness of the applied film and the composition, and examples thereof include 100 ° C. to 200 ° C., 30 seconds to 5 minutes, and the like.

  As a method for forming a coating film on these textiles, direct printing such as screen printing, thermal transfer printing, or the like can be applied. Thermal transfer printing is a method of forming a coating film by applying a textile ink on a release paper or the like and then heat-pressing the gelled film obtained by heating to the textile. The coating film formed on the textile is solidified by heating. The heating conditions can be appropriately selected depending on the thickness of the applied film and the composition, and examples thereof include 100 ° C. to 200 ° C., 30 seconds to 5 minutes, and the like.

  Hereinafter, the present invention will be described in detail with reference to examples.

[Example 1] Synthesis of acrylic polymer particles A1 Into a 5 liter four-necked flask equipped with a thermometer, a nitrogen gas introduction tube, a stirring rod, a dropping funnel and a cooling tube, 952 g of pure water was placed for 60 minutes. Nitrogen gas was passed through to replace dissolved oxygen in pure water. After stopping nitrogen gas ventilation, 45.6 g of methyl methacrylate and 34.9 g of n-butyl methacrylate were added, and the temperature was raised to 80 ° C. while stirring at 180 rpm. When the internal temperature reached 80 ° C., 0.70 g of potassium persulfate dissolved in 35 g of pure water was added at once, and soap-free polymerization was started. Stirring was continued for 60 minutes at 80 ° C. to obtain a seed particle dispersion.

  Subsequently, a monomer emulsion (methyl methacrylate 637.0 g, n-butyl methacrylate 343.0 g, glycidyl methacrylate 7.0 g, sodium dialkylsulfosuccinate (trade name: Perex O, manufactured by Kao Corporation) was added to the seed particle dispersion. -TP) 9.80 g and 350.0 g of pure water mixed and stirred for emulsification) was added dropwise over 3.5 hours, followed by continued stirring at 80 ° C. for 1 hour to obtain the first dropped polymer. A dispersion was obtained.

  Subsequently, 0.84 g of potassium persulfate was added to this first dropping polymer dispersion, and further a monomer emulsion (methyl methacrylate 392.6 g, methacrylic acid 27.4 g, sodium dialkylsulfosuccinate (manufactured by Kao Corporation) , Product name: PELEX O-TP) 8.2 g and 350.0 g of pure water mixed and stirred for emulsification) was added dropwise over 1.5 hours, followed by continuing stirring at 80 ° C. for 1 hour, A second dropping polymer dispersion was obtained.

  After cooling the obtained second dropping polymer dispersion to room temperature, an inlet temperature of 170 ° C., an outlet temperature of 75 ° C., and an atomizer rotational speed are used by using a spray dryer (manufactured by Okawara Chemical Co., Ltd., type L-8). Acrylic polymer fine particles A1 were obtained by spray drying at 25000 rpm.

[Example 1] Preparation of plastisol composition 100 parts by mass of BET (manufactured by LG Chemical Co., Ltd.) and 100 parts by mass of acrylic polymer particles A1 as plasticizers were put into a plastic container, and a vacuum mixer (Sinky Corporation) After mixing and stirring at atmospheric pressure for 10 seconds using ARV-200), the pressure was reduced to 20 mmHg, mixing and stirring was continued for 90 seconds, and defoamed to obtain a uniform plastisol. The storage stability of the obtained plastisol was evaluated by the following method. Furthermore, a coating film was formed using this, and the strength and elongation were measured.

[Viscosity after mixing]
Within 3 hours after the preparation of plastisol, the viscosity was measured at a measurement temperature of 25 ° C. and a rotation speed of 10 rpm using a Brookfield type viscometer (manufactured by Toki Sangyo Co., Ltd., BH type viscometer, No. 7 rotor). Was used as the viscosity after mixing.
A: 10000 mPa · s or less ○: 10000 mPa · s or more and less than 30000 mPa · s ×: 30000 mPa · s or more [Storage stability]
Within 3 hours after the preparation of plastisol, the viscosity was measured at a measurement temperature of 25 ° C. and a rotation speed of 5 rpm using a Brookfield viscometer (manufactured by Toki Sangyo Co., Ltd., BH viscometer, No. 7 rotor). Was the initial viscosity. The temperature was kept in a constant temperature bath at 40 ° C., taken out after 10 days, and the viscosity was measured again under the same conditions. The viscosity increase rate S of plastisol was calculated from the following formula (unit:%), and the storage stability was evaluated according to the following criteria based on the calculated value. The results are shown in Table 3.

S = [(viscosity after storage / initial viscosity) -1] × 100 (%)
A: Less than 150 B: 150 or more and less than 250 x: Gelation from 250 or more.

[Strength of coating film]
The plastisol obtained on a glass plate on which release paper was laid was applied to a thickness of 2 mm and gelled by heating at 130 ° C. for 20 minutes to obtain a uniform coating film. The coating film of plastisol peeled from the release paper was punched into a dumbbell No. 2 type (JIS K6251) and used as a test piece. About this test piece, the test temperature is 25 ° C., the test speed is 200 mm / min. Under the above conditions, a tensile test was conducted with a Tensilon universal testing machine, and the strength of the coating film was evaluated from the maximum point stress value according to the following criteria. The results are shown in Table 3.
Strength (unit: MPa)
A: 3.5 or more O: Less than 4.0 3.0 or more Δ: Less than 3.5 2.5 or more ×: Less than 2.5

[Elongation of coating film]
In the tensile test, the elongation of the coating film was evaluated according to the following criteria from the value of the elongation at break. The results are shown in Table 3.
Elongation (unit:%)
A: 400 or more B: Less than 400 300 or more x: 300 or less.

[Elastic modulus of coating film]
In the tensile test, the elastic modulus of the coating film was evaluated according to the following criteria from the value of the maximum point stress. The results are shown in Table 3.
A: 3 MPa or less B: 3 MPa or more and less than 5 MPa X: 5 MPa or more [Tack of coating film]
About the obtained coating film, visual observation was performed and tack was evaluated according to the following criteria. The results are shown in Table 3.

A sample is cut into a length of 150 mm and a width of 150 mm, and this is used as a test piece. After stacking two test pieces, they are sandwiched between glass plates, and a 5 kg weight is placed on the uppermost glass plate so as not to be displaced, and left at 25 ° C. for 3 hours. After the lapse of the specified time, the test piece was taken out from the glass plate, and the degree of peeling of the test piece was evaluated.
A: Easily peelable ○: Peelable ×: Difficult or impossible to peel [Examples 2 to 4, Comparative Examples 1 to 4] Preparation of plastisol Table 1 shows Example 1 except that a plasticizer was used. Similarly, plastisol was prepared, its storage stability was evaluated, a coating film was formed, and the strength, elongation, elastic modulus and tack of the coating film were evaluated. Table 1 shows the content of the compound represented by the formula (1) in plastisol, and Table 2 shows the evaluation results.

(Note) The numbers in the table indicate parts by mass.
“ATBC”: a citrate plasticizer manufactured by Dainippon Ink and Chemicals, Inc. (trade name “Monocizer ATBC”)
“W-23S”: a polyester plasticizer manufactured by Dainippon Ink & Chemicals, Inc. (trade name “Polysizer W-23S”)
“TXIB”: Aliphatic ester plasticizer manufactured by Eastman Chemical Co., Ltd. (trade name: TXIB)
“UP1021”: Acrylic oligomer plasticizer manufactured by Toagosei Co., Ltd. (trade name “ARUFON UP-1021”)

  From the results, it is clear that the plastisol of the present invention is excellent in strength, elongation and elasticity and excellent in tackiness.

Claims (3)

A plastisol comprising polymer particles and a trimethylolpropane ester represented by the formula (1), wherein the content of the trimethylolpropane ester is 20% by mass or more and 80% by mass or less.

(In the formula, R ₁ to R ₃ independently represent a hydrocarbon group.)   The plastisol according to claim 1, wherein the polymer particles are acrylic polymer particles.   A textile ink comprising the plastisol according to claim 2.