JP5192470B2 - Paste resin composition - Google Patents

Description

  The present invention relates to a paste resin composition. The paste resin composition of the present invention can be used in various applications depending on the type of synthetic resin. For example, it is a general purpose such as wallpaper, flooring cushion floor, ceiling interior material, etc .; toys, gloves, leather, etc. Articles; automotive materials such as sealing materials and undercoat materials; and other applications such as steel plate coating and canvas coating.

  As a synthetic resin used for the paste resin composition, for example, a vinyl chloride resin is often used. When vinyl chloride resin is used as a synthetic resin, for example, resin powder of vinyl chloride resin, plasticizer, diluent, thickener, filler such as calcium carbonate, pigment, flame retardant, foaming agent, stabilizer Etc. are blended to prepare a paste resin composition. However, many paste resin compositions have a high viscosity and are often difficult or impossible to process.

  As a method for improving such a high viscosity, conventionally, a hydrocarbon solvent such as mineral spirit, alkylbenzene, paraffin or the like is used as a diluent or a thinning agent, or an anionic surfactant, a polysiloxane is used as a thinning agent. Oxyethylene alkylphenol ether, polyethylene glycol, sorbitan ester, glycerin alkyl ester, etc. are used. These diluents and thickeners are added after the production of the synthetic resin and when preparing the paste resin composition, but the thinning effect is not sufficient, especially when fillers such as calcium carbonate are blended The viscosity drop was not sufficient.

  In addition, the paste resin composition is gelled by heating or the like in the processing step for application to various uses, but when the hydrocarbon-based diluent is used, the paste resin composition is gelled. The diluent sometimes volatilizes in the atmosphere, which is not preferable from the viewpoint of environment and cost.

  The total number of carbon atoms obtained from fatty acids and aliphatic alcohols as additives for the above-mentioned insufficient viscosity-reducing effect, viscosity stability over time, processability such as volatilization of diluent, environmental issues, and economic issues. It has been proposed to use a fatty acid ester having 5 to 35 and / or a (poly) alkylene glycol mono or dialkyl ether having an alkyl group with 1 to 8 carbon atoms (Patent Document 1).

JP 2001-335696 A

  In recent years, however, awareness of required properties and environmental problems has increased, and a composition for paste resin having a lower viscosity and a lower volatile content has been demanded. Furthermore, since these resin compositions for pastes are also suitably used for wallpaper, it has become necessary to reduce odor.

  An object of the present invention is to provide a paste resin composition that has a large viscosity-reducing effect even when a filler such as calcium carbonate is blended, has very little volatilization of a diluent, and can further reduce odor.

That is, the present invention relates to (B) general formula (1): R ¹ —O—R ² (wherein R ¹ and R 1) with respect to 100 parts by weight of (A) synthetic resin (hereinafter also referred to as component (A)). ² independently represents a paste resin composition containing 1 to 30 parts by weight of a dialkyl ether (hereinafter also referred to as component (B)) represented by a C 5-10 alkyl group.

  Since the paste resin composition of the present invention uses the component (B) as a diluent, it is excellent in workability because of its excellent viscosity reducing effect even when a filler such as calcium carbonate is blended. In addition, since the paste resin composition of the present invention uses the component (B) as a diluent, a commonly used hydrocarbon-based diluent can be omitted. At the time of processing, and further after the processing is completed, volatilization of organic substances (reduction of VOC) and generation of odor can be suppressed, environmental pollution can be reduced, and the economy is excellent.

  Examples of the synthetic resin used as the component (A) used in the paste resin composition of the present invention include vinyl chloride resins; acrylic resins such as methacrylic resins and ethylene / acrylic copolymer resins, and ethylene / vinyl acetate based resins. Examples thereof include resins. Among these, as the component (A), a vinyl chloride resin is preferable. As the vinyl chloride-based resin, in particular, from the viewpoint of the viscosity reducing effect and the odor reduction by the interaction with the dialkyl ether which is the component (B) in the present invention, vinyl chloride alone or a monomer copolymerizable therewith is used. A mixture having an average particle size of 0.1 to 50 μm obtained by emulsion polymerization or microsuspension polymerization and an average degree of polymerization of 700 to 4000 is preferable. Examples of the monomer copolymerizable with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid, acrylic acid and the like.

  The vinyl chloride resin is usually obtained as a resin latex, but in the paste resin composition of the present invention, the resin latex is dried from the viewpoint of practical use. As for other synthetic resins, those obtained as resin latex are spray-dried.

In the present invention, as the diluent, the component (B), which is the general formula (1): R ¹ —O—R ² (wherein R ¹ and R ² are each independently alkyl having 5 to 10 carbon atoms) A dialkyl ether represented by the following formula: In the general formula (1), R ¹ and R ² may be the same or different. In the component (B), the carbon number of the alkyl group according to R ¹ and R ² is 5 to 10, and the alkyl group having 5 or more carbon atoms suppresses volatilization of organic substances and generation of odor. be able to. Moreover, when the said alkyl group is 10 or less, the function as a diluent is exhibited and the viscosity reducing effect is exhibited. The alkyl group according to R ¹ and R ² preferably has an alkyl group having 6 to 10 carbon atoms, and more preferably an alkyl group having 7 to 10 carbon atoms. Further, from the viewpoint, the total number of carbon atoms in the alkyl group of ^{R 1} and ^{R 2} is 10 to 20, the total number of carbon atoms is preferably from 12 to 20, further more preferably 14 to 20. The alkyl group may be either a straight chain or a branched chain, but the straight chain has a boiling point higher than that of the branched chain, and from the viewpoint of suppressing the volatilization of organic substances and the generation of odor, the straight chain alkyl group Is preferred. The component (B) preferably has a boiling point of 200 ° C. or higher from the viewpoint of suppressing the volatilization of organic substances and generation of odors, and the boiling point is 350 ° C. or lower from the viewpoint of the stability of the chemical structure. Is preferred.

  In addition, the freezing point of the component (B) functions effectively as a diluent in the production of the paste resin composition, and can easily dissolve the component (A) and finish the production in a short time. From the viewpoint of suppressing the deterioration of quality due to the efficiency of the property and the occurrence of the protrusion, the freezing point at 1013 hPa is preferably 20 ° C. or less. The freezing point is more preferably 10 ° C. or lower. On the other hand, the freezing point is preferably −60 ° C. or higher, more preferably −20 ° C. or higher, from the viewpoint of suppressing volatilization of organic substances and generation of odor. The freezing point is measured based on JIS K6750.

  Specific examples of the component (B) include, for example, di-n-pentyl ether, diamyl ether, di-n-hexyl ether, di-n-heptyl ether, di-n-octyl ether, di-n-nonyl ether, di-2-ethylhexyl. Examples include ether, di-n-decyl ether, and di-n-hexyl ether, di-n-heptyl ether, and di-n-octyl ether are preferable from the viewpoint of suppressing volatilization of organic substances and generation of odor. As the component (B), one type may be used alone, or two or more types may be mixed and used.

  The compounding quantity of (B) component in the paste resin composition of this invention is 1-30 weight part with respect to 100 weight part of (A) component. Component (B) has a viscosity reducing effect on the synthetic resin according to component (A) in the blending amount in the above range, and is preferable from the viewpoint of the performance of the final product such as wallpaper. From the above viewpoint, the blending amount of the component (B) is preferably 2 to 20 parts by weight, more preferably 3 to 20 parts by weight, and further 5 to 20 parts by weight with respect to 100 parts by weight of the component (A). Is preferred.

  In addition to the component (A) and the component (B), the paste resin composition of the present invention includes (C) a polyoxyalkylene alkyl ether having 8 to 20 carbon atoms in the alkyl group or alkenyl group and the carbon number in the alkyl group. Can contain at least one selected from the group consisting of 8 to 20 polyoxyalkylene alkyl ether carboxylates (hereinafter also referred to as component (C)). By adding the component (C) to the paste resin composition, the effect of reducing the viscosity is improved, so that the coating property is improved, and even when the filler is blended, the dispersibility of the filler is improved and the coating is good. It is thought to show gender.

  The freezing point of the component (C) shows the thinning effect, and can be finished in a short time in the production of the paste resin composition. From the viewpoint of suppression, the freezing point at 1013 hPa is preferably 20 ° C. or lower. The freezing point is more preferably 10 ° C. or lower.

Among the components (C), the polyoxyalkylene alkyl ether having 8 to 20 carbon atoms in the alkyl group or alkenyl group (hereinafter referred to as the (C1) component) is an alcohol having 8 to 20 carbon atoms and 2 to 2 carbon atoms. It can be synthesized by adding 3 alkylene oxides. The alkyl group may be linear or branched. The alkyl group is preferably an alkyl group or alkenyl group having 10 to 20 carbon atoms, and more preferably an alkyl group or alkenyl group having 12 to 18 carbon atoms, from the viewpoint of a thinning effect. Examples of the alkylene oxide include ethylene oxide and propylene oxide. When two or more alkylene oxides are used, the repeating unit of the polyoxyalkylene structure may be either a block body or a random body. Moreover, 1-10 are preferable from a viewpoint of the viscosity reduction effect of a paste resin composition, and, as for the average addition mole number of the alkylene oxide based on the repeating unit of a polyoxyalkylene structure, 2-7 are more preferable. The average added mole number is determined from the difference between the molecular weight of the polyoxyalkylene alkyl ether and the molecular weight of the ether. The molecular weight of 1 mol of the polyoxyalkylene alkyl ether is determined by dividing 56.1 (molecular weight of potassium hydroxide) by the hydroxyl value (mg / KOHg) determined according to JIS K0070.
Molecular weight of 1 mol of polyoxyalkylene ether = 56100 / hydroxyl value of polyoxyalkylene ether

  Specific examples of the component (C1) include polyoxyethylene decyl ether, polyoxyethylene oxypropylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene oxypropylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene oxypropylene Examples include stearyl ether.

  Further, among the (C) component, the polyoxyalkylene alkyl ether carboxylate having an alkyl group having 8 to 20 carbon atoms (hereinafter referred to as the (C2) component) is obtained by replacing the (C1) component obtained as described above. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used to form an alcoholate, and then a halogenated carboxylate such as sodium chloroacetate is reacted to dehalogenate the alkali metal (eg, desalinate). Can be synthesized.

  Specific examples of the component (C2) include polyoxyethylene lauryl ether carboxylate, polyoxyethylene myristyl ether carboxylate, polyoxyethylene decyl ether carboxylate, polyoxyethylene stearyl ether carboxylate and the like.

  As the component (C), one type may be used alone, or two or more types may be mixed and used. As the component (C), polyoxyethylene lauryl ether carboxylate and polyoxyethylene myristyl ether carboxylate are particularly preferable.

  The blending amount of the component (C) in the paste resin composition of the present invention is preferably 5 parts by weight or less, and 0.05 parts by weight or more with respect to 100 parts by weight of the component (A). preferable. The component (C) has a viscosity reducing effect on the synthetic resin according to the component (A) in the blending amount in the above range, and is preferable from the viewpoint of cost or performance of the final product. From these viewpoints, the amount of component (C) is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, relative to 100 parts by weight of component (A). More preferably.

  Moreover, a plasticizer and a filler can be added to the paste resin composition of the present invention.

  Examples of the plasticizer include dioctyl phthalate (DOP) and diisononyl phthalate (DINP), as well as phthalic acid having 1 to 13 carbon atoms such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and diundecyl phthalate. Esters: Trimellitic acid esters of alcohols having 6 to 10 carbon atoms, such as trioctyl trimellitic acid, tridecyl trimellitic acid; adipic acid esters, azelaic acid esters, sebacic acid esters, phosphoric acid esters, polyesters , Epoxy type, fatty acid ester type, pyromellitic acid ester type plasticizer and the like. A plasticizer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  It is preferable that the compounding quantity of the plasticizer in the paste resin composition of this invention is 10-150 weight part with respect to 100 weight part of (A) component. The said compounding quantity of a plasticizer is preferable from the point of the viscosity of a paste resin composition. From the above viewpoint, the amount of the plasticizer is preferably 30 to 130 parts by weight, more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the component (A).

  Examples of the filler used in the present invention include calcium carbonate, talc, silica, clay, calcium silicate, and alumina. A filler may be used individually by 1 type and may be used in mixture of 2 or more types.

  It is preferable that the compounding quantity of the filler in the paste resin composition of this invention is 10-400 weight part with respect to 100 weight part of (A) component. The said compounding quantity of a filler is preferable from the point of the viscosity of a paste resin composition. From the above viewpoint, the filler content is preferably 50 to 300 parts by weight, more preferably 100 to 200 parts by weight, per 100 parts by weight of component (A).

  Furthermore, the paste resin composition according to the present invention is, in addition to the above-mentioned components, additives such as a foaming agent, a stabilizer, a lubricant, a flame retardant, an antioxidant, a colorant, and an ultraviolet absorber that are usually added to the paste resin composition. Can be appropriately blended.

  The paste resin composition of the present invention is prepared by adding the component (B) and, if necessary, the component (C) to the component (A). The method for adding the component (B) and the component (C) is not particularly limited, and can be carried out by blending the components (A) sequentially or sequentially. In preparing the paste resin composition, when the preparation is solid or pasty, the preparation can be appropriately heated to the melting point or higher and the components (B) and (C) can be added. . In preparing the paste resin composition of the present invention, a plasticizer, a filler, and other additives are appropriately blended.

  In preparing the paste resin composition of the present invention, a commonly used stirring and dispersing device such as a ribbon blender, a super mixer, a disper, or a dissolver can be used.

Example 1
100 parts by weight of vinyl chloride resin (ZESTPQ84: manufactured by Shin-Daiichi PVC Co.), 10 parts by weight of di-n-hexyl ether as component (B) as a diluent, DINP as a plasticizer (Vinizer 90: manufactured by Kao Corporation) 50 parts by weight, calcium carbonate (Whiteon H: manufactured by Toyo Fine Chemical Co., Ltd.) 100 parts by weight, titanium oxide 15 parts by weight, and as other additives, a tin-based stabilizer (ADK STAB FL44: manufactured by Asahi Denka Kogyo Co., Ltd.) 3 parts by weight Parts and 3 parts by weight of a foaming agent (Vinifer AC # 1C: manufactured by Eiwa Kasei Kogyo Co., Ltd.) were added and uniformly stirred and dispersed with a laboratory mixer, and then defoamed under vacuum to prepare a vinyl chloride paste resin composition.

Examples 2-7
In Example 1, in the same manner as in Example 1 except that the type and blending amount of the component (B) and the component (C) were further changed as shown in Table 1 when the component (C) was further contained. A vinyl chloride paste resin composition was prepared.

Comparative Examples 1-7
In Example 1, instead of the component (B), the type and amount of diluent shown in Table 1 were used, and when the component (C) is further contained, the type and amount are shown in Table 1. A vinyl chloride paste resin composition was prepared in the same manner as in Example 1 except that the above was changed. However, in Comparative Example 7, neither a diluent nor a component (C) is blended.

  The following evaluation was performed on the vinyl chloride paste resin compositions obtained in Examples and Comparative Examples. The results are shown in Table 1.

(1) Viscosity of paste resin composition (hereinafter referred to as B-type viscosity)
After being left in a constant temperature and humidity room at 23 ° C. and a relative humidity of 60% for 2 hours, the Brookfield BL type viscometer (manufactured by Tokyo Keiki Co., Ltd.) Using four rotors, the measurement was performed at a rotational speed of 60 r / min (6 r / min when the B-type viscosity is 10,000 mPa · s or more).

(2) Volatile content The prepared paste resin composition was developed on a glass plate (length x width x height = 20 cm x 15 cm x 2 mm) with a coating amount of 1 mm, and left in an oven at 200 ° C for 5 minutes. The gel was gelled, and the weight change rate was determined by the following formula, and this was defined as the volatile content (%).
Weight change rate (%) = {(weight of base resin composition before gelation−weight of base resin composition after gelation) / weight of base resin composition before gelation} × 100

(3) Odor About the prepared paste resin composition, the odor was evaluated in the following four stages in a room adjusted to 23 ° C.
4: No odor at all.
3: There is almost no odor.
2: There is some odor.
1: There is a strong odor.

In Table 1, the boiling point of component (B) used in the examples and the freezing point at 1013 hPa are:
Di-n-hexyl ether: boiling point 227 ° C., freezing point −40 ° C.,
Di-n-octyl ether: boiling point 314 ° C., freezing point −10 ° C.,
Di-n-decyl ether: boiling point 350 ° C. or higher, freezing point 12 ° C.,
The boiling point of the diluent used in the comparative example and the freezing point at 1013 hPa are
Mineral spirit: boiling point 225 ° C, freezing point -40 ° C
Di-n-butyl ether: boiling point 141 ° C., freezing point −98 ° C.,
Di-n-dodecyl ether: boiling point 350 ° C. or higher, freezing point 32 ° C.
(C) component is
POE (9) L: polyoxyethylene (average addition mole number is 9) lauryl ether: freezing point: 20 ° C.
POE (4.5) LEC: polyoxyethylene (average addition mole number is 4.5) lauryl ether carboxylate: freezing point: 0 ° C.

  As is clear from Table 1, since the examples use the dialkyl ether according to the component (B) as a diluent, compared with Comparative Example 7 where no diluent is used, the viscosity reducing effect is large. In addition, it can be seen that the diluent volatilization is extremely small, and further the odor can be reduced. On the other hand, in Comparative Examples 1 to 4, mineral spirit is used as a diluent, and a thinning effect is recognized as compared with Comparative Example 7 in which a diluent is not used, but there is much volatilization of the diluent and the odor is reduced. It has not been reduced. In Comparative Example 5, dialkyl ether is used as the diluent, and a viscosity reducing effect is recognized as compared with Comparative Example 7 in which the diluent is not used, but the carbon number of the alkyl group is smaller than that of the component (B). It is small and has a lot of diluent volatilization, and the odor cannot be reduced. In Comparative Example 6, dialkyl ether is used as a diluent, and there is a thickening effect as compared with Comparative Example 7 in which no diluent is used, but the carbon number of the alkyl group is larger than the component (B), The thinning effect is not sufficient. In Example 1 and Comparative Example 1, a diluent having a similar boiling point is used. However, Example 1 has much less volatile matter and odor than Comparative Example 1, and vinyl resin and It turns out that the remarkable effect by the combination with the dialkyl ether which concerns on (B) component can be expressed.

Claims (4)

(A) For 100 parts by weight of the synthetic resin, (B) General formula (1): R ¹ —O—R ² (wherein R ¹ and R ² are each independently an alkyl group having 5 to 10 carbon atoms) are shown. dialkyl ethers containing 1 to 30 parts by weight represented by), the synthetic resin is a vinyl resin der Ru paste resin composition chloride. Further, the (A) relative to the synthetic resin 100 parts by weight, (C) an alkyl group having carbon atoms of polyoxyalkylene alkyl ether and the alkyl group having 8 to 20 carbons 8-20 polyoxyalkylene alkyl ether carboxylate The paste resin composition according to claim 1, which contains at least one selected from the group consisting of 0.05 parts by weight and 5 parts by weight.   Furthermore, the paste resin composition of Claim 1 or 2 which contains 10-150 weight part of plasticizers, and 10-400 weight part of filler with respect to 100 weight part of said (A) synthetic resins.   The paste resin composition according to claim 1, wherein the dialkyl ether (B) has a freezing point at 1013 hPa of −60 ° C. or higher and 20 ° C. or lower.