JP2012136605A - Polyvinyl chloride composite resin aqueous composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasticized polyvinyl chloride-based film which generates no cracks even if being applied and dried as an aqueous dispersion; and to provide a film, a molded body and the like causing no bleedout.SOLUTION: An aqueous composite resin composition is obtained by mixing an aqueous dispersion (A) of a modified polyvinyl chloride resin particle and an aqueous dispersion (B) of a polyurethane resin particle, wherein (A)/(B) is in the range of 50/50 to 80/20 in weight ratio in terms of resin solid content; and the aqueous dispersion (A) of a modified polyvinyl chloride resin particle is obtained by copolymerizing a monomer (a1) containing a hydroxyl group and a vinyl group, and a vinyl chloride monomer (a2), and (a1)/(a2) is in the range of 2/98 to 20/80 in weight ratio.

Description

  The present invention relates to an aqueous composite resin composition obtained by mixing an aqueous dispersion of modified polyvinyl chloride resin particles and an aqueous dispersion of polyurethane resin particles.

  Since vinyl chloride resin is excellent in quality balance, it is used in various fields such as coatings, paints, leathers, hoses, wire covering materials, and building materials. However, the vinyl chloride resin does not give flexibility to the vinyl chloride resin unless a plasticizer such as di-2-ethylhexyl phthalate (DOP) is used. There was a problem that the agent migrated to the resin surface. For this reason, some proposals have been made to solve the bleed-out while imparting plasticity by compounding a polyurethane resin with a vinyl chloride resin.

(1) Graft polymer of vinyl chloride resin and thermoplastic polyurethane resin.
A method for producing a soft thermoplastic resin by suspension polymerization (graft copolymerization) of a thermoplastic polyurethane soluble in a vinyl chloride monomer and a vinyl chloride monomer has been proposed (for example, see Patent Document 1). In this method, since it is necessary to dissolve the thermoplastic polyurethane in the vinyl chloride monomer and uniformly mix it, the composition and blending amount of the thermoplastic polyurethane must be restricted. In addition, in the application of paints and coating agents, there is a problem from the viewpoints of environmental problems and occupational health because a soft thermoplastic resin is dissolved in an organic solvent.

(2) Formation of polyurethane resin in vinyl chloride resin.
A method for producing a polyvinyl chloride-polyurethane composite by impregnating a polyol into a powder or granular vinyl chloride resin, adding a polyisocyanate to this under stirring, and forming a polyurethane resin in the vinyl chloride resin has been proposed. (For example, refer to Patent Document 2). In this method, since the raw material is naturally diffused in the solid vinyl chloride resin, the restriction of the raw material composition and the generation of the polyurethane resin become non-uniform, leading to gelation of polyurethane and a decrease in mechanical strength. In addition, in paint and coating agent applications, it is necessary to dissolve in an organic solvent, which causes environmental problems and occupational health problems.

(3) Formation of a polyurethane resin in a molten state in a vinyl chloride resin.
There has been proposed a method for producing a polyvinyl chloride-polyurethane composite in which a mixture of a polyvinyl chloride resin, a polyol and a polyisocyanate is heated and melted under a shearing force to form polyurethane under the molten state of polyvinyl chloride (for example, patents). Reference 3). In this method, when excessive shearing force is applied, decomposition of the vinyl chloride resin and gelation of the polyurethane resin occur, deterioration of workability at the time of molding, poor appearance of the molded body, mechanical properties, etc. occur. The composition and blending amount of the polyurethane resin are limited. In addition, when used as a paint or a coating agent, it must be dissolved in an organic solvent, resulting in environmental problems and occupational health problems.
(4) A blend of an aqueous dispersion of polyurethane resin particles and an aqueous dispersion of polyvinyl chloride resin.
A composite resin aqueous dispersion composition obtained by blending an aqueous polyurethane resin dispersion and an aqueous polyvinyl chloride resin dispersion at a constant weight ratio has been proposed (see, for example, Patent Document 4). According to this document, when this composite resin aqueous dispersion is used as an adhesive, the adhesion to various adhesives is improved and the adhesive strength is improved. However, when this is used as a paint / coating agent, the compatibility between the polyvinyl chloride resin and the polyurethane resin is not sufficient, and especially when the ratio of the polyvinyl chloride resin is high, the coating film after drying is cracked. was there.

Japanese Patent Publication No. 60-30688 Japanese Patent Publication No.59-39464 Japanese Patent Publication No. 07-91456 Japanese Patent Laid-Open No. 10-273587

  The present invention has been made in view of the above-described background art, and an object of the present invention is to provide an aqueous composite resin composition capable of forming a plasticized polyvinyl chloride film without cracking even when applied and dried. Furthermore, it is to provide an aqueous composite resin composition capable of forming a film or a molded body that does not cause bleed out.

  As a result of intensive studies to solve the above problems, the present inventors have found an aqueous composite resin composition containing specific modified polyvinyl chloride resin particles and polyurethane resin particles, and obtained by drying it. The present inventors have found that a molded body such as a film, a film, and a sheet that can solve the above-mentioned problems, and have completed the present invention.

  That is, the present invention is an aqueous composite resin composition, a composite resin composition obtained therefrom, and a molded body thereof as described below.

  [1] An aqueous composite resin composition obtained by mixing an aqueous dispersion (A) of modified polyvinyl chloride resin particles and an aqueous dispersion (B) of polyurethane resin particles, wherein (A) / (B ) Is in the range of 50/50 to 80/20 in terms of weight ratio in terms of resin solids, and the aqueous dispersion (A) of the modified polyvinyl chloride resin particles contains a hydroxyl group and a vinyl group. It is obtained by copolymerizing the body (a1) and the vinyl chloride monomer (a2), and (a1) / (a2) is in the range of 2/98 to 20/80 by weight ratio. An aqueous composite resin composition characterized by that.

  [2] The monomer (a1) containing a hydroxyl group and a vinyl group is a hydroxyl group-containing (meth) acrylic acid ester represented by the following formula (1) or (2), represented by the following formula (3) or (4): 1 or 2 or more compounds selected from the group consisting of the hydroxyl group-containing vinyl ethers shown and the hydroxyl group-containing allyl ethers represented by the following formula (5) or (6) ] The aqueous composite resin composition as described in.

［上記式（１）中、Ｒ_１は水素原子又はメチル基を表し、ｎは１〜１０の整数を表す。］

[In the above formula (1), _{R 1} represents a hydrogen atom or a methyl group, n represents an integer of 1 to 10. ]

［上記式（２）中、Ｒ_１は水素原子又はメチル基を表し、ｎは１〜１０の整数を表す。］

[In the above formula (2), _{R 1} represents a hydrogen atom or a methyl group, n represents an integer of 1 to 10. ]

［上記式（３）中、ｎは１〜１０の整数を表す。］

[In said formula (3), n represents the integer of 1-10. ]

［上記式（４）中、ｎは１〜１０の整数を表す。］

[In said formula (4), n represents the integer of 1-10. ]

［上記式（５）中、ｎは１〜１０の整数を表す。］

[In said formula (5), n represents the integer of 1-10. ]

［上記式（６）中、ｎは１〜１０の整数を表す。］
［３］ポリウレタン樹脂粒子の水性分散体（Ｂ）が、ポリイソシアネート成分（ｂ１）、ポリオール成分（ｂ２）、及び活性水素を有する親水基含有化合物（ｂ３）を反応させて、プレポリマーを合成した後、乳化することで得られるものであることを特徴とする上記［１］又は［２］に記載の水性複合樹脂組成物。

[In said formula (6), n represents the integer of 1-10. ]
[3] The aqueous dispersion (B) of polyurethane resin particles reacted with the polyisocyanate component (b1), the polyol component (b2), and the hydrophilic group-containing compound (b3) having active hydrogen to synthesize a prepolymer. Thereafter, the aqueous composite resin composition according to [1] or [2], which is obtained by emulsification.

  [4] A composite resin composition obtained by drying the aqueous composite resin composition according to any one of [1] to [3].

  [5] A molded body of a composite resin composition obtained by drying and molding the aqueous composite resin composition according to any one of [1] to [3].

  The film of the composite resin composition obtained by drying the aqueous composite resin composition of the present invention has excellent characteristics due to the polyurethane resin such as abrasion resistance while maintaining the characteristics of the polyvinyl chloride resin. , Coatings, paints, sealing agents, leathers, hoses, wire coatings and the like.

  Also, by drying and molding the aqueous composite resin composition of the present invention, it is possible to obtain molded products such as films and sheets that are excellent in moldability and mechanical properties and have no plasticizer bleed out.

2 is a photograph showing the shape of a film molded body obtained in Example 1. FIG. 2 is a photograph showing the shape of a film molded body obtained in Comparative Example 1.

  Hereinafter, the present invention will be described in detail.

The aqueous composite resin composition of the present invention is
An aqueous composite resin composition obtained by mixing an aqueous dispersion (A) of modified polyvinyl chloride resin particles and an aqueous dispersion (B) of polyurethane resin particles, wherein (A) / (B) is: The weight ratio in terms of resin solid content is in the range of 50/50 to 80/20, and the aqueous dispersion (A) of modified polyvinyl chloride resin particles is a monomer containing a hydroxyl group and a vinyl group (a1 ) And vinyl chloride monomer (a2) are copolymerized, and (a1) / (a2) has a weight ratio of 2/98 to 20/80. Features.

  First, the aqueous dispersion (A) of modified polyvinyl chloride resin particles used in the present invention will be described.

  The aqueous dispersion (A) of modified polyvinyl chloride resin particles used in the present invention comprises a normal suspension of a monomer (a1) containing a hydroxyl group and a vinyl group and a vinyl chloride monomer (a2). It can prepare by copolymerizing using superposition | polymerization, emulsion polymerization, and seed polymerization.

  The aqueous dispersion of the modified vinyl chloride resin used in the present invention comprises a monomer (a1) containing a hydroxyl group and a vinyl group and a vinyl chloride monomer (a2) [single quantity containing a hydroxyl group and a vinyl group. It is obtained by reacting in the range of 2/98 to 20/80 as the weight ratio of the body (a1)] / [vinyl chloride monomer (a2)]. When the weight ratio of (a1) / (a2) is 2/98 or more, the moldability of the aqueous composite resin composition is improved, and when it is 20/80 or less, not only the moldability but also the mechanical properties are improved. To do.

  As the monomer (a1) containing a hydroxyl group and a vinyl group used in the present invention, a hydroxyl group-containing (meth) acrylic acid ester represented by the above formula (1) or (2), the above formula (3) or One or more compounds selected from the group consisting of the hydroxyl group-containing vinyl ethers represented by (4) and the hydroxyl group-containing allyl ethers represented by the above formula (5) or (6) are preferably used. . In the above formula, when n is 10 or less, the moldability and mechanical properties of the resulting aqueous composite resin composition are improved.

  Examples of the hydroxyl group-containing (meth) acrylic acid ester represented by the above formula (1) or (2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meta). ) Acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyoctyl (meth) acrylate, and the like.

  Examples of the hydroxyl group-containing vinyl ether represented by the above formula (3) or (4) include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 3-hydroxybutyl vinyl ether. , 2-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether and the like.

  Examples of the hydroxyl group-containing allyl ether represented by the above formula (5) or (6) include 2-hydroxyethyl (meth) allyl ether, 3-hydroxypropyl (meth) allyl ether, 2-hydroxypropyl (meth) allyl. Ether, 4-hydroxybutyl (meth) allyl ether, 3-hydroxybutyl (meth) allyl ether, 2-hydroxy-2-methylpropyl (meth) allyl ether, 5-hydroxypentyl (meth) allyl ether, 6-hydroxyhexyl (Meth) allyl ether etc. are mentioned.

  The number average molecular weight of the polyvinyl chloride resin thus obtained is preferably in the range of 10,000 to 200,000.

  Next, the aqueous dispersion (B) of the polyurethane resin used in the present invention will be described.

  The aqueous dispersion (B) of polyurethane resin particles used in the present invention is obtained, for example, by a reaction of a polyisocyanate component (b1), a polyol component (b2), and a hydrophilic group-containing compound (b3) having active hydrogen. . Specifically, it is preferable to emulsify the prepolymer after reacting the polyisocyanate component (b1), the polyol component (b2), and the hydrophilic group-containing compound (b3) having active hydrogen.

  As the polyisocyanate component (b1) used in the present invention, various aliphatic, alicyclic and aromatic isocyanate compounds which are usually available can be used.

  Examples of the aliphatic polyisocyanate include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, And dimer acid diisocyanate.

  Examples of the alicyclic polyisocyanate include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (isophorone). Diisocyanate), bis- (4-isocyanatocyclohexyl) methane (hydrogenated MDI), norbornane diisocyanate and the like.

  Examples of the aromatic polyisocyanate include diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 3,3′-dimethyl-4,4′-diisocyanate. Biphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, α, α, α ′, Examples include α′-tetramethylxylylene diisocyanate.

  In the present invention, the polyol means a compound containing two or more hydroxyl groups having reactivity with an isocyanate group.

  As the polyol component (b2) used in the present invention, various polyester polyols, polycarbonate polyols, polycarbonate polyols, polyether polyols, low molecular polyols having a molecular weight of less than 400, and the like that are usually available can be used.

  Examples of polyester polyols include condensed polyester polyols, polycarbonate polyols, and polylactone polyols.

  Examples of the condensed polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6- Dioxanes such as hexanediol, neopentyl glycol, butylethylpropane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, and succinic acid, adipic acid, azelaic acid, sebacic acid, Dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarbo Reaction products of dicarboxylic acids such as acid. Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentylene adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, poly (polytetramethylene ether) ) Adipate condensation polyester diols such as adipate diol, and azelate condensation polyester diols such as polyethylene azelate diol and polybutylene azelate diol.

  Examples of the polycarbonate polyol include a reaction product of the diols and dialkyl carbonates such as dimethyl carbonate. Specifically, polytetramethylene carbonate diol, poly 3-methylpentamethylene carbonate diol, polyhexamethylene carbonate diol and the like are exemplified.

  Examples of the polylactone polyol include ε-caprolactone, γ-butyrolactone, γ-valerolactone, and a ring-opening polymer of a mixture of two or more of these, and specific examples include polycaprolactone diol. The

  Examples of the polyether polyol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, catechol, hydroquinone, bisphenol A, and the like. Examples include a reaction product obtained by addition polymerization of monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene using a compound having at least two hydrogen atoms as an initiator. When two or more types of monomers are subjected to addition polymerization, block addition, random addition, or a mixed system of both may be used. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like.

  Examples of the low molecular polyol having a molecular weight of less than 400 include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Aliphatic diols such as hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, polyfunctional aliphatic polyols such as glycerin, trimethylolpropane, pentaerythritol, 1,4-cyclohexanediol, 1,4 -Cyclohexanedimethanol, alicyclic diols such as hydrogenated bisphenol A, aromatic diols such as bisphenol A, hydroquinone and bishydroxyethoxybenzene, polyols of these alkylene oxide adducts, etc. It is. A low molecular polyol having a molecular weight of less than 400 is generally used for the purpose of adjusting physical properties.

  As the hydrophilic group-containing compound (b3) having active hydrogen used in the present invention, for example, a diol having a carboxyl group can be used. Specifically, 2,2-dimethylolpropionic acid, 2, Examples include 2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, and the like. Moreover, the carboxylic acid group containing polyester polyol manufactured by using these as a part of raw material can also be used suitably. Furthermore, a polyester polyol having a sulfonic acid group introduced by 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, or the like may be used. By neutralizing these hydrophilic group-containing compounds having active hydrogen introduced with hydrophilic groups with organic amines such as ammonia and triethylamine, metal bases such as Na, K, and Li, the resulting polyurethane resin is submerged in water. Can be dispersed.

  In the present invention, a hydrophilic group-containing compound having an amino group as active hydrogen can also be used. For example, sodium 2- (2-aminoethylamino) ethanesulfonate, 2-acrylamido-2-methylpropanesulfone Examples include sodium salts of lysates of acid and ethylenediamine, lysine, 1,3-propylenediamine-β-ethylsulfonic acid, and the like.

  In the present invention, when the prepolymer is synthesized by reacting the polyisocyanate component (b1), the polyol component (b2), and the hydrophilic group-containing compound (b3) having active hydrogen, the reaction proceeds uniformly. An organic solvent inert to an isocyanate group such as acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, dioxane, tetrahydrofuran may be added during or after the reaction.

  When the prepolymer contains a hydrophilic group capable of forming a salt such as a carboxylic acid group or a sulfonic acid group, it is desirable to make it hydrophilic (neutralized) using a neutralizing agent. As the neutralizing agent, for example, a basic compound can be used. Specifically, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, trimethylamine, triethylamine, triethylenediamine, dimethylaminoethanol, N-methyl Examples thereof include tertiary amines such as morpholine, aqueous ammonia and the like.

  The hydrophilization (neutralization) method is not particularly limited. For example, (1) a method of reacting with a neutralizing agent before, during or after synthesis of the prepolymer, (2) during emulsification Examples include a method of adding a neutralizing agent to the water to be used.

  In the present invention, the aqueous dispersion (B) of polyurethane resin particles is, for example, phase inversion emulsification for obtaining an aqueous polyurethane resin while dispersing water in the prepolymer, or emulsifying a prepolymer in water containing a nonionic surfactant. It is obtained by an emulsification method such as forced emulsification to obtain a water-based polyurethane resin.

  As the surfactant used for emulsification, a nonionic surfactant is generally used. For example, polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc. Polyoxyethylene alkyl phenyl ether, ethylene oxide adduct of acetylene diol, polyoxyethylene derivative, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, polyethylene glycol fatty acid ester, polyoxyethylene laurylamine, and other polyoxyethylene An alkylamine etc. are mentioned.

  The method for adding the nonionic surfactant is not particularly limited, and examples thereof include (1) a method of adding before emulsification, and (2) a method of adding with water used during emulsification.

  In the present invention, it is desirable to add a chain extender before emulsification, during emulsification or after emulsification to increase the molecular weight of the prepolymer. In the present invention, the chain extender refers to water or a polyamine compound containing two or more primary or secondary amino groups. High molecular weight of the prepolymer can be achieved by extending the remaining isocyanate group of the prepolymer with a chain extender. Examples of such polyamine compounds include ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, xylylenediamine, metaphenylenediamine, piperazine, hydrazine, and adipic acid dihydrazide.

  When the aqueous dispersion (B) of polyurethane resin particles contains a low-boiling organic solvent, it is desirable to distill off the organic solvent at 30 to 80 ° C. under reduced pressure. Moreover, it is also possible to adjust the resin solid content concentration in the aqueous polyurethane resin composition by adding or distilling off water.

  In this invention, when manufacturing the aqueous dispersion (B) of a polyurethane resin particle, a crosslinking agent can also be mix | blended in order to improve durability further. The crosslinking agent may be a commonly used one and is not particularly limited. Examples thereof include amino resins, epoxy compounds, aziridine compounds, carbodiimide compounds, and oxazoline compounds.

  Next, the aqueous composite resin composition of the present invention will be described.

  The aqueous composite resin composition of the present invention is obtained by mixing an aqueous dispersion (A) of modified polyvinyl chloride resin particles and an aqueous dispersion (B) of polyurethane resin particles, The aqueous dispersion of vinyl chloride resin particles (A) / the aqueous dispersion of polyurethane resin particles (B)] is in the range of 50/50 to 80/20 in terms of weight ratio in terms of resin solid content. By setting the weight ratio in terms of resin solid content of (A) / (B) to 50/50 or more, the mechanical properties of the obtained molded body are improved, and by setting it to 80/20 or less, cracking of the molded body is caused. Formability and mechanical properties are improved without the occurrence.

  In the present invention, the method of mixing the aqueous dispersion of modified polyvinyl chloride resin particles (A) and the aqueous dispersion of polyurethane resin particles (B) is not particularly limited, Examples thereof include mixing and dispersion using a magnetic costar, and mixing and dispersion using a homogenizer.

  In the aqueous composite resin composition of the present invention, if necessary, thickeners such as carboxymethyl cellulose, hydrophilic group-containing synthetic resin emulsion, urethane-modified polyether thickener, modified polyacrylic acid thickener, phenolic anti-aging Additives such as additives, hindered amine antioxidants, thioether antioxidants, silicone-based antistatic agents and mold release agents, inorganic fillers such as colloidal silica, colorants, pigments, lubricants, etc. It may be added as a compounding agent.

  In the present invention, when the aqueous composite resin composition contains a low-boiling organic solvent, it is desirable to distill off the organic solvent at 30 to 80 ° C. under reduced pressure. Moreover, it is also possible to adjust the resin solid content concentration in the aqueous composite resin composition by adding or distilling off water.

  By drying the aqueous composite resin composition of the present invention, a molded body such as a film or a sheet can be obtained.

  Specifically, after immersing the mold in the aqueous composite resin composition of the present invention, the mold is taken out, and the aqueous polyurethane resin composition attached to the surface is heated and dried to form a film or sheet. can do. Moreover, a coating film can be obtained by apply | coating the aqueous composite resin composition of this invention to surfaces, such as a metal and wood, and drying. Furthermore, after the aqueous composite resin composition of the present invention is dried by an extruder and pelletized, a molded body can be obtained using an injection molding machine or an extrusion molding machine.

  The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

  In addition, the evaluation method of the film which shape | molded the aqueous composite resin composition in the following Examples and Comparative Examples after drying and it was as follows.

<Measuring method of average particle diameter>
The average particle size of each of the aqueous dispersion of polyurethane resin particles and the aqueous dispersion of modified polyvinyl chloride resin particles was measured by using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.) and setting the refractive index of the dispersion medium to 1.33. The diameter distribution was measured to determine the median particle diameter, and the average particle diameter of each resin particle was determined.

<Drying method>
(Modified) An aqueous composite resin composition obtained by mixing an aqueous dispersion of polyvinyl chloride resin particles and an aqueous dispersion of polyurethane resin particles is cast on a glass casting plate and dried at 130 ° C. The film was dried for 10 minutes to obtain a dry film.

<Moldability>
The surface state of the dried film was observed for cracks and cracks.

<Measurement of film strength>
The dried film was hot press molded at 5 ° C. for 2 minutes at 170 ° C., and the film was conditioned in a temperature-controlled room and punched with a JIS No. 4 dumbbell to obtain a test piece. The test piece was subjected to a tensile test at a tensile speed of 200 (mm / min) using a tensile tester (manufactured by Toyo Baldwin Co., Ltd., Tensilon UTM-4-100 type).

<Plasticizer bleed-out test>
The dried film was inserted into a ferro plate and allowed to stand at 70 ° C. for 7 days, and then the presence or absence of bleed on the ferro plate surface was observed.

Preparation Example 1 Preparation of an aqueous dispersion of modified polyvinyl chloride resin particles.
In a 2.5 L polymerization can, 800 g of deionized water, 21 g of 2-hydroxypropyl acrylate, 679 g of vinyl chloride monomer, 0.6 g of lauroyl peroxide, 4 g of 15 wt% potassium laurate aqueous solution, and 15 wt% dodecylbenzenesulfonic acid 10 g of an aqueous sodium solution was charged, and the temperature was raised to 56 ° C. to proceed the polymerization. After the pressure decreases, unreacted vinyl chloride monomer is recovered, and an aqueous dispersion of modified polyvinyl chloride resin particles having a K value of 67 and an average particle size of 0.15 μm (hereinafter referred to as “polymer A”). )

Preparation Example 2 Preparation of aqueous dispersion of polyvinyl chloride resin particles.
In a 2.5 L polymerization vessel, 720 g of deionized water, 600 g of vinyl chloride monomer, 0.6 g of lauroyl peroxide, and 60 g of a 15 wt% sodium dodecylbenzenesulfonate aqueous solution were charged, and the polymerization solution was mixed for 75 minutes with a homomixer. After the homogenization treatment, the temperature was raised to 64 ° C. to proceed the polymerization. After the pressure is reduced, the unreacted vinyl chloride monomer is recovered to obtain an aqueous dispersion of polyvinyl chloride resin particles having a K value of 63 and an average particle size of 0.8 μm (hereinafter referred to as “polymer B”). )

Preparation Example 3 Preparation of aqueous dispersion of polyurethane resin particles.
<Synthesis of urethane prepolymer solution>
In a reactor equipped with a reflux condenser, 64.3 g of diphenylmethane diisocyanate (manufactured by Nippon Polyurethane, Millionate MT-F) and 16.1 g of 1,6-hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry) as a polyisocyanate component, poly as a polyester polyol 100 g of butylene adipate (manufactured by Nippon Polyurethane, Nipponporan 4010), 100 g of polyethylene adipate (manufactured by Nippon Polyurethane, Nipponporan 4040), 3.7 g of dimethylolpropionic acid, 15.7 g of neopentyl glycol, 1.2 g of trimethylolpropane, and methyl ethyl ketone 128 g was added to prepare a prepolymer organic solvent solution having a solid content of 70% by weight at a reaction temperature of 80 (° C.).

<Synthesis of aqueous dispersion of polyurethane resin particles>
In a homogenizer (TK. Homomixer MARKII, manufactured by PRIMIX), pure water 60 g, caustic soda 0.22 g, nonionic emulsifier polyoxyethylene lauryl ether (manufactured by NOF Corporation, K220) 1.08 g, antifoaming agent (manufactured by San Nopco, Deformer 440) Dispersed water containing 0.3 g was placed in an emulsifying tank and emulsified and circulated at a stirring speed of 6000 rpm. Thereafter, 100 g of a prepolymer organic solvent solution having a solid content of 70% by weight and further diluted with methyl ethyl ketone to a solid content of 60% by weight was added dropwise for 5 minutes to 10 minutes, followed by emulsification circulation. The emulsion was circulated for 10 minutes to mature the polyurethane emulsion. In the chain extension reaction, a chain extender solution in which 0.6 g of piperazine was dissolved in water was added to the aqueous urethane emulsion in the emulsification tank while stirring with a magnetic costar. Then, the organic solvent was distilled off from the aqueous urethane emulsion in the emulsifying tank while stirring under reduced pressure at 45 ° C. using an evaporator to obtain an aqueous dispersion of polyurethane resin particles (hereinafter referred to as “polymer C”). It was.

Example 1.
Polymer A and polymer C adjusted to be 30 parts by weight of modified polyvinyl chloride resin with respect to 70 parts by weight of polyurethane resin as the solid content of the resin are placed in a 100 mL beaker and stirred with a magnetic stirrer for 30 minutes to form an aqueous composite resin Compositions were prepared and evaluated as described above. The results are shown in Table 1.

表１及び図１から明らかなとおり、実施例１の水性複合樹脂組成物を加熱乾燥して得られたフィルム成型体は、シート成型性が良く、機械強度に優れ、可塑剤のブリードアウトがなかった。

As is apparent from Table 1 and FIG. 1, the film molding obtained by heating and drying the aqueous composite resin composition of Example 1 has good sheet moldability, excellent mechanical strength, and no plasticizer bleed-out. It was.

Example 2 and Example 3.
An aqueous composite resin composition was prepared under the same conditions as in Example 1 except that the blend ratio shown in Table 1 was changed using Polymer A and Polymer C, and evaluated as described above. The results are also shown in Table 1.

  As is clear from Table 1, the film moldings obtained by heating and drying the aqueous composite resin compositions of these examples had good sheet moldability, excellent mechanical strength, and no plasticizer bleed out.

Comparative Examples 1 to 3
An aqueous composite resin composition was prepared under the same conditions as in Example 1 except that the polymer B and polymer C were used and the blend ratio shown in Table 1 was used, and evaluation was performed as described above. The results are also shown in Table 1.

  As is clear from Table 1 and FIG. 2, the film moldings obtained by heating and drying the aqueous composite resin compositions of these comparative examples had poor sheet moldability and poor mechanical strength, although there was no bleeding out of the plasticizer.

Comparative Example 4
Disperser (TK Disper type) prepared by blending 45 parts by weight of a plasticizer (dioctyl terephthalate) and 3 parts by weight of a stabilizer (zinc stearate) with respect to 100 parts by weight of the resin solid content, using the polymer B. SL, manufactured by Koki Kako), defoamed and then heat-dried to obtain a molded polyvinyl chloride film. In this molded body, the plasticizer bleeded out.

Claims (5)

An aqueous composite resin composition obtained by mixing an aqueous dispersion (A) of modified polyvinyl chloride resin particles and an aqueous dispersion (B) of polyurethane resin particles, wherein (A) / (B) is: The weight ratio in terms of resin solid content is in the range of 50/50 to 80/20, and the aqueous dispersion (A) of the modified polyvinyl chloride resin particles is a monomer containing a hydroxyl group and a vinyl group (a1 ) And a vinyl chloride monomer (a2), wherein (a1) / (a2) is in a range of 2/98 to 20/80 by weight. An aqueous composite resin composition. The monomer (a1) containing a hydroxyl group and a vinyl group is a hydroxyl group-containing (meth) acrylic acid ester represented by the following formula (1) or (2), a hydroxyl group represented by the following formula (3) or (4) 2. The compound according to claim 1, wherein the compound is one or more compounds selected from the group consisting of a vinyl ether containing and a hydroxyl group-containing allyl ether represented by the following formula (5) or (6): An aqueous composite resin composition.

[In the above formula (1), _{R 1} represents a hydrogen atom or a methyl group, n represents an integer of 1 to 10. ]

[In the above formula (2), _{R 1} represents a hydrogen atom or a methyl group, n represents an integer of 1 to 10. ]

[In said formula (3), n represents the integer of 1-10. ]

[In said formula (4), n represents the integer of 1-10. ]

[In said formula (5), n represents the integer of 1-10. ]

[In said formula (6), n represents the integer of 1-10. ]. The aqueous dispersion (B) of polyurethane resin particles is obtained by reacting a polyisocyanate component (b1), a polyol component (b2), and a hydrophilic group-containing compound (b3) having active hydrogen. The aqueous composite resin composition according to claim 1 or 2. A composite resin composition obtained by drying the aqueous composite resin composition according to any one of claims 1 to 3. A molded body of a composite resin composition obtained by drying and molding the aqueous composite resin composition according to any one of claims 1 to 3.

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