JP2007031664A - Low viscosity paste resin composition - Google Patents

Abstract

[PROBLEMS] A vinyl chloride paste resin composition, particularly a system containing an inorganic compound, has a high viscosity reducing effect, little viscosity change over time, and a wide range of viscosity reducing effects from high shear rate to low shear rate. The present invention provides a low-viscosity paste resin composition containing a thinning agent having low volatility and high safety.
SOLUTION: 1.0 to 10 parts by mass of ethylene glycol monoalkyl ether fatty acid ester or 1.0 to 10 parts by mass of ethylene glycol monoalkyl ether fatty acid ester with respect to 100 parts by mass of resin for vinyl chloride paste A paste resin composition comprising 1.0 to 10 parts by mass of an aliphatic monoalcohol fatty acid ester.
[Selection figure] None

Description

  The present invention relates to a low-viscosity paste resin composition used for wallpaper, toys, flooring materials, gloves, sealing materials, and the like, and more particularly to a vinyl chloride paste resin composition.

  The paste resin composition comprises a resin powder obtained by spray drying a resin latex obtained by emulsion polymerization or microsuspension polymerization of a monomer such as vinyl chloride, and a plasticizer (usually dioctyl phthalate (DOP) or diisononyl phthalate (DINP)). ), Inorganic compounds such as diluents, calcium carbonate (also called fillers), pigments, flame retardants, stabilizers, etc., blended with calendering, extruder processing, rotational molding Various processing methods such as molding processing such as slush molding and dip molding, spread processing, and spray processing are used depending on the application.

Many paste resin compositions have a problem that liquid viscosity becomes high and processing is difficult because a large amount of an inorganic compound is added for the purpose of cost reduction and rigidity improvement.
In order to solve this problem, a viscosity reducing agent that lowers the liquid viscosity is used for the purpose of improving workability and workability in processing the paste resin composition. In general, alkylbenzene, mineral spirits, hydrocarbon compounds such as paraffin, anionic surfactants, polyoxyethylene alkylphenol ethers, sorbitan fatty acid esters, glycerin fatty acid esters, and the like are known as thickeners.

  As the mainstream of thickeners, hydrocarbon compound-based thickeners have been widely used due to cost and performance, but VOC (Volatile Organic Compounds) is a major problem because of recent environmental considerations. It has become to. In particular, VOC is identified as a causative substance of sick house in wallpaper processed using a paste resin composition, and the countermeasures are being promoted.

  As a non-hydrocarbon viscosity reducing agent for a vinyl chloride paste resin composition, a polyhydric alcohol condensed hydroxy fatty acid ester (for example, see Patent Document 1), a polyglycerol condensed ricinoleic acid ester (for example, see Patent Document 2), carbon number A combination of an ester of a fatty acid having 1 to 20 and an aliphatic alcohol having 1 to 20 carbon atoms and having a total carbon number of 5 to 35 and a polyoxyalkylene alkyl ether having an alkyl group having 8 to 20 carbon atoms (for example, However, it is not satisfactory with respect to a wide range of thinning effect and cost from a low shear rate to a high shear rate, and further improvement has been desired.

JP-A-11-130893 Japanese Patent Laid-Open No. 9-324090 JP 2001-335696 A

  The problem of the present invention is that the vinyl chloride paste resin composition, particularly in a system containing an inorganic compound, has a high viscosity reducing effect, little change in viscosity over time, and has a viscosity reducing effect at high shear rate and low shear rate. An object of the present invention is to provide a low-viscosity paste resin composition containing a thickening agent that is high and less volatile.

（式中、Ｒ₁は炭素数１〜８の脂肪族１価アルコール残基、Ｒ₂は炭素数７〜１７の脂肪酸残基。）
２．塩化ビニル系ペースト樹脂１００質量部に対して、粘度低下剤としてエチレングリコールモノアルキルエーテル脂肪酸エステルを１．０〜１０質量部、炭素数が８〜１８の脂肪酸と炭素数が１〜１８の脂肪族１価アルコールの脂肪族モノアルコール脂肪酸エステル（以下Ｂ成分という）を１．０〜１０質量部含有することを特徴とする塩化ビニル系ペースト樹脂組成物。
３．Ａ成分の合計炭素数が１８〜２８であり、Ｂ成分の合計炭素数が１８〜３６であることを特徴とする上記１及び２に記載の塩化ビニル系ペースト樹脂組成物。
４．塩化ビニル系ペースト樹脂１００質量部に対して可塑剤が２０〜１２０質量部、無機物質が１０〜２００質量部を含有することを特徴とする上記１、２及び３に記載の塩化ビニル系ペースト樹脂組成物。 As a result of intensive studies on the above problems, the present inventors have been able to solve the problem by the following method.
1. It contains 1.0 to 10 parts by mass of an ethylene glycol monoalkyl ether fatty acid ester represented by the following formula (hereinafter referred to as component A) as a viscosity reducing agent with respect to 100 parts by mass of the vinyl chloride paste resin. Vinyl chloride paste resin composition.

(In the formula, R ₁ is an aliphatic monohydric alcohol residue having 1 to 8 carbon atoms, and R ₂ is a fatty acid residue having 7 to 17 carbon atoms.)
2. 1.0 to 10 parts by mass of an ethylene glycol monoalkyl ether fatty acid ester as a viscosity reducing agent, a fatty acid having 8 to 18 carbon atoms and an aliphatic having 1 to 18 carbon atoms with respect to 100 parts by mass of the vinyl chloride paste resin A vinyl chloride paste resin composition containing 1.0 to 10 parts by mass of an aliphatic monoalcohol fatty acid ester of a monohydric alcohol (hereinafter referred to as component B).
3. 3. The vinyl chloride paste resin composition according to 1 and 2 above, wherein the total carbon number of the A component is 18 to 28 and the total carbon number of the B component is 18 to 36.
4). 4. The vinyl chloride paste resin according to the above 1, 2 and 3, wherein the plasticizer contains 20 to 120 parts by mass and the inorganic substance contains 10 to 200 parts by mass with respect to 100 parts by mass of the vinyl chloride paste resin. Composition.

By using the product of the present invention, a vinyl chloride paste resin composition, particularly a system containing an inorganic compound, exhibits an excellent thinning effect over a wide range from a high shear rate to a low shear rate, and the viscosity over time. A stable paste resin composition with little change was obtained.
Further, even when the paste resin composition was molded, the sheet surface condition and bleeding property were not adversely affected as compared with the conventional product.

[About this thinning agent]
The component A ethylene glycol monoalkyl ether fatty acid ester used in the present invention is an ester obtained by esterifying ethylene glycol monoalkyl ether and a fatty acid having 8 to 18 carbon atoms. The ethylene glycol monoalkyl ether used here is obtained by adding 1 mol of ethylene oxide to 1 mol of aliphatic monohydric alcohol. The aliphatic monohydric alcohol is a monohydric alcohol having 1 to 8 carbon atoms, and specifically includes methanol, ethanol, propanol, n-butanol, n-hexanol, n-octanol, 2-ethylhexanol and the like. Can be mentioned. The ethylene glycol monoalkyl ether fatty acid ester obtained by using an alcohol having 10 or more carbon atoms is inferior in handleability because it solidifies at a low temperature such as winter.
Specific examples of ethylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monooctyl ether Etc.
Examples of fatty acids used in the esterification reaction include commercially available caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and isostearic acid. In the case of a fatty acid having less than 8 carbon atoms, the boiling point is low and it tends to volatilize. Fatty acids having more than 18 carbon atoms are not preferred because they have poor dispersibility when mixed with the vinyl chloride paste resin composition, and the viscosity reducing effect of the vinyl chloride paste resin composition is inferior.

According to the classification by boiling point by the World Health Organization, VOC is defined as 50-100 ° C to 240-260 ° C.
The ethylene glycol monoalkyl ether fatty acid ester having the smallest molecular weight of the component A is ethylene glycol monomethyl ether caprylic acid ester (total carbon number 11). Ethylene glycol monoalkyl ether fatty acid esters having a boiling point of 240 to 260 ° C. or higher are preferred in terms of esters that do not fall within the definition of VOC by the World Health Organization classification. For this reason, ethylene glycol monoalkyl ethers having a total carbon number of 18 or more Fatty acid esters are preferred.
In consideration of the dispersibility with respect to the vinyl chloride paste resin composition, the surface state of the wallpaper after molding, etc., the total carbon number of the ethylene glycol aliphatic monoalcohol ether fatty acid ester is preferably up to 28.

  The method of synthesizing ethylene glycol monoalkyl ether fatty acid ester (component A) is prepared by adding ethylene glycol monoalkyl ether and fatty acid in equimolar amounts, adding no catalyst, or using a catalyst such as alkali, acid, metal compound, etc. It can be easily obtained by carrying out an esterification reaction in the range of ° C.

The fatty acid of the aliphatic monoalcohol fatty acid ester which is the component B of the present invention has 8 to 18 carbon atoms, and is generally commercially available caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid Oleic acid, linoleic acid, isostearic acid and the like. Fatty acids having more than 18 carbon atoms are not preferred because they have poor dispersibility when mixed with vinyl chloride paste resin.
The aliphatic monohydric alcohol is a monohydric alcohol having 1 to 18 carbon atoms, such as methanol, ethanol, propanol, n-butanol, n-hexanol, n-octanol, 2-ethylhexanol, decanol, lauryl alcohol. , Myristyl alcohol, palmityl alcohol, oleyl alcohol and the like. A monohydric alcohol having more than 18 carbon atoms is not preferable because of its poor dispersibility when mixed with a vinyl chloride paste resin. Moreover, the viscosity reducing effect of the vinyl chloride paste resin is inferior.

The aliphatic monoalcohol fatty acid ester having the smallest molecular weight among the B component is methyl caprylate (total carbon number 9), but the total carbon number is 18 or more in terms of an ester that does not enter VOC according to the classification of the World Health Organization. The aliphatic monoalcohol fatty acid esters are preferred.
Further, esters of fatty acids having more than 18 carbon atoms and aliphatic monoalcohols having more than 18 carbon atoms have poor dispersibility when mixed with the vinyl chloride paste resin, and are inferior in the viscosity reducing effect of the vinyl chloride paste resin. Therefore, the total carbon number of the B component is more preferably 18 to 36.

  Aliphatic monoalcohol fatty acid ester (component B) is synthesized by adding equimolar amounts of fatty acid and alcohol, and adding no catalyst or adding acid, alkali, metal oxide, etc. as a catalyst, and esterifying at a high temperature of 150 to 250 ° C. Can be easily obtained.

  The component A according to the present invention can obtain a thinning effect even if it is added alone to the vinyl chloride paste resin composition, but the thinning effect, cost, and physical properties of the final product of the vinyl chloride paste resin composition. In view of the above, it is preferable to add 1.0 to 10 parts by mass of component A and 1.0 to 10 parts by mass of component B with respect to 100 parts by mass of the vinyl chloride paste resin. When the blending amount exceeds 10 parts by mass for both the A component and the B component, stickiness is seen on the surface after molding, which is not preferable. On the other hand, if it is less than 1.0 part by mass, the effect of the present invention cannot be obtained. In order to obtain a higher viscosity reducing effect in a wide range from a low shear rate to a high shear rate, it is preferable to use the A component and the B component in combination. The ratio is preferably A component / B component = 100/0 to 10/90, more preferably 80/20 to 30/70.

[Vinyl chloride paste resin composition]
The vinyl chloride paste resin composition of the present invention contains a vinyl chloride paste resin, a plasticizer, a stabilizer, an inorganic compound, and the like, and the viscosity reducer of the present invention.

The vinyl chloride paste resin used in the present invention is a polyvinyl chloride or vinyl copolymer having a number average polymerization degree of about 600 to about 2,000. Examples of vinyl copolymers include polyvinylidene chloride, copolymers of vinyl chloride and monomers such as ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid, and acrylic acid.
Polyvinyl chloride resin is most widely used for paste formulation, and a vinyl monomer having a polymerization degree of 600 to 2000 obtained as a nearly spherical shape of 0.1 μm to 50 μm by emulsion polymerization or fine particle suspension polymerization is used. Vinyl chloride paste resin is preferred.

  Examples of the plasticizer used in the present invention include phthalic acid compounds such as DOP (dioctyl phthalate) and DINP (diisononyl phthalate), aromatic polybasic acid esters such as trioctyl trimellitate, DOA (dioctyl adipate), DINA ( Dibasic acid compounds such as diisononyl adipate), tribasic acid compounds such as citric acid and trimellitic acid, phosphoric acid compounds, fatty acid esters such as octyl oleate, and epoxy systems such as epoxidized soybean oil Examples thereof include compounds and acetylated monoglycerides. The blending amount of the plasticizer is preferably 20 parts by mass to 120 parts by mass with respect to 100 parts by mass of the polyvinyl chloride paste resin from the viewpoint of the performance of the final product.

  Examples of the stabilizer used in the present invention include metal soap-based Ba / Zn-based, Ca / Zn-based, Sn-based stabilizer, and Pb-based stabilizer.

The inorganic compound used in the present invention generally includes calcium carbonate, but other examples include talc, kaolin clay, mica, silica, alumina, and barium sulfate. The addition amount of the inorganic compound is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the polyvinyl chloride paste resin from the viewpoint of the viscosity reducing effect and the performance of the final product.
When a foaming agent is blended, azodicarboxylic acid amide (ADCA) is generally used as the foaming agent, but other examples include azobisisobutylnitrile (AIBN) and dinitrosopentamethylenetetramine (DPT).

  In addition to the above components, the vinyl chloride paste resin composition of the present invention can appropriately contain a diluent, a lubricant, a flame retardant, an antioxidant, an antistatic agent, an ultraviolet absorber, and the like.

  The vinyl chloride paste resin composition of the present invention can be obtained by adding the above additives to a vinyl chloride paste resin and stirring with a commonly used ribbon blender, super mixer, disper, dissolver, or the like. Thus, the obtained paste resin composition has little increase in viscosity over time and has a low environmental load.

  EXAMPLES Hereinafter, although an Example is given and this invention product is demonstrated more concretely, these Examples do not restrict | limit this invention.

[Preparation of Examples and Comparative Samples]
For the ethylene glycol monoalkyl ether fatty acid ester which is the component A of the present invention, ethylene glycol monobutyl ether or ethylene glycol monooctyl ether was used as the ethylene glycol monoalkyl ether. As the fatty acid moiety, lauric acid or oleic acid was used.
Ethylene glycol monobutyl ether lauric acid ester (Table 1, A-1) and ethylene glycol monobutyl ether oleic acid ester (Table 1, A-2) are composed of 1 mol of ethylene glycol monobutyl ether (total carbon number 6) and lauric acid (carbon 12) or 1 mol of oleic acid (18 carbon atoms) was charged into a four-necked flask, and the mixture was heated and mixed in an inert gas stream at 165 ° C. for 10 hours under an alkali catalyst to carry out an esterification reaction. After completion of the reaction, it was neutralized with an acid equimolar to the alkali catalyst, and diatomaceous earth filtration was performed.
Similarly, ethylene glycol monooctyl ether oleic acid ester (Table 1, A-3) is a 4-neck flask containing 1 mol of ethylene glycol monooctyl ether (total carbon number 10) and 1 mol of oleic acid (carbon number 18). The mixture was heated and mixed at 175 ° C. for 8 hours in an inert gas stream under an alkali catalyst to carry out an esterification reaction. After completion of the reaction, it was neutralized with an acid equimolar to the alkali catalyst, and diatomaceous earth filtration was performed.
About the raw material used, the commercial item was used.
Details of the reaction products are summarized in Table 1.

About the aliphatic monoalcohol fatty acid ester which is the B component of the present invention, Exepal M-OL (manufactured by Kao Corporation) was used as the methanol oleate (Table 2, B-1). 2-ethylhexanol oleic acid ester (Table 2, B-2) was charged with 1 mol of 2-ethylhexanol (carbon number 8) and 1 mol of oleic acid (carbon number 18) in a 4-necked flask, and an inert gas stream. The esterification reaction was carried out by heating and mixing at 170 ° C. for 10 hours with no catalyst. Oleyl alcohol oleic acid ester (Table 2, B-3) was prepared by charging 1 mol of oleyl alcohol (18 carbon atoms) and 1 mol of oleic acid (18 carbon atoms) into a four-necked flask, and using an inert gas stream, no catalyst Then, the mixture was heated and mixed at 190 ° C. for 8 hours to carry out esterification.
About the raw material used, the commercial item was used.
Details of the reaction products are summarized in Table 2.

For other comparative samples, the following were used.
Comparative product 1: Ethylene glycol monodecanyl ether oleate (total carbon number 30)
1 mol of ethylene glycol monodecanyl ether (1 mol of 1-decanol added with 1 mol of ethylene oxide) and 1 mol of oleic acid were charged into a four-necked flask at 190 ° C under an inert gas stream without catalyst. The mixture was heated and mixed for 9 hours to carry out an esterification reaction.

Comparative product 2: Ethylene glycol monobutyl ether caproate (total carbon number: 12)
1 mol of ethylene glycol monobutyl ether and 1 mol of caproic acid were charged into a four-necked flask, and an esterification reaction was carried out by heating and mixing at 165 ° C. for 12 hours in an inert gas stream under an alkali catalyst. After completion of the reaction, it was obtained by neutralizing with an equimolar acid with an alkali catalyst and performing diatomaceous earth filtration.

Comparative product 3: behenylbehenate (44 carbon atoms)
1 mol of behenyl alcohol (22 carbon atoms) and 1 mol of behenic acid (22 carbon atoms) were charged into a four-necked flask and heated and mixed at 245 ° C. for 12 hours in an inert gas stream without any catalyst to perform esterification. .

[Examples 1 to 10 and Comparative Examples 1 to 6]
ZEST PQB83 (polymerization degree 700; manufactured by Shin-Daiichi PVC Co., Ltd.) as a polyvinyl chloride resin, DINP (produced by Daihachi Chemical Co., Ltd.) and DINA (manufactured by Sanken Chemical Co., Ltd.), calcium carbonate, titanium oxide, Ba / A base blend was prepared by blending a Zn stabilizer and an ADCA foaming agent in the ratios shown in Table 3 below.
A polyvinyl chloride paste resin composition was prepared by adding a thinning agent to the above base formulation and mixing and defoaming at 700 rpm for 10 minutes with a stirrer capable of vacuum defoaming.
The blending ratio is summarized in Table 3.
Table 4 shows prescription contents of each example, and Table 5 shows prescription contents of each comparative example.

  For the prepared vinyl chloride paste resin composition, the viscosity (initial viscosity and time-dependent viscosity), observation of the dispersion state after molding (confirmation of foamed cell state), and confirmation of the surface state of the molded product (presence of stickiness) are as follows. Carried out.

(1) Regarding the viscosity, the polyvinyl chloride paste resin composition after defoaming was stored for 2 hours and 3 days at 25 ° C., and No. of Brookfield BL type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Using 4 rotors, the viscosity was measured at 6 rpm and 60 rpm.
However, on the instrument, a viscosity of 100,000 mPa · s or more at 6 rpm and 10,000 mPa · s or more at 60 rpm cannot be measured.

(2) Regarding the dispersed state after molding, a composition that has been passed for 24 hours after adjustment of the paste resin is poured into a predetermined size molding frame (vertical / horizontal = 150/130 mm) to a thickness of about 0.5 mm. The gel was stored in a dryer at 230 ° C. for 2 minutes to form a sheet.

The state of dispersion of the surface of the sheet was observed with the naked eye to confirm the foamed cell state.
[Criteria]
◎: Dispersibility is good, uniform surface dispersion ○: Dispersion failure is observed in a very small part Δ: Dispersion failure is partially observed ×: Dispersion failure is observed

(3) As for the surface state of the molded product, the sheet produced in the above (2) was stored in a storage at 25 ° C., and the sticky state of the surface after 1 week was evaluated by feeling.
[Criteria]
◎: No stickiness △: Slightly sticky ×: Stickiness

  The evaluation results of each example are summarized in Table 6, and the evaluation results of each comparative example are summarized in Table 7.

(4) The evaluation of the volatility of the thinning agent is performed using a differential thermothermal gravimetric simultaneous measurement device (TG / DTA6200) manufactured by Seiko Denshi Kogyo Co., Ltd. at a temperature range of 30 to 300 ° C. at an air flow rate of 200 ml / min. The temperature was raised at a rate of ° C./min, and the sample weight reduction rate at that time was measured. The evaluation results are shown in Table 8.

  From the results of Tables 6 and 7, in the examples of the present invention, the viscosity of the paste resin can be reduced, and a significant improvement in workability can be expected. In addition, a molded article having an excellent surface condition can be obtained. Moreover, from the volatility result of Table 8, there is little volatilization at the molding temperature (around 200 ° C.), and a low volatility paste resin is obtained.

From the above results, according to the present invention, in the paste resin composition system, particularly in the system in which the inorganic compound is blended, the viscosity reducing effect is high, the viscosity change with time is small, the safety itself is high, and the blending cost is reduced. Therefore, an object of the present invention is to provide a paste resin composition containing a thinning agent which is effective and low in volatility with a low addition amount.

Claims (4)

It contains 1.0 to 10 parts by mass of an ethylene glycol monoalkyl ether fatty acid ester represented by the following formula (hereinafter referred to as component A) as a viscosity reducing agent with respect to 100 parts by mass of the vinyl chloride paste resin. Vinyl chloride paste resin composition.

(In the formula, R ₁ is an aliphatic monohydric alcohol residue having 1 to 8 carbon atoms, and R ₂ is a fatty acid residue having 7 to 17 carbon atoms.)   1.0 to 10 parts by mass of an ethylene glycol monoalkyl ether fatty acid ester as a viscosity reducing agent, a fatty acid having 8 to 18 carbon atoms and an aliphatic having 1 to 18 carbon atoms with respect to 100 parts by mass of the vinyl chloride paste resin A vinyl chloride paste resin composition containing 1.0 to 10 parts by mass of an aliphatic monoalcohol fatty acid ester of a monohydric alcohol (hereinafter referred to as component B).   The total carbon number of A component is 18-28, and the total carbon number of B component is 18-36, The vinyl chloride paste resin composition of Claim 1 and 2 characterized by the above-mentioned. 4. The vinyl chloride paste according to claim 1, wherein the plasticizer contains 20 to 120 parts by mass and the inorganic substance contains 10 to 200 parts by mass with respect to 100 parts by mass of the vinyl chloride paste resin. Resin composition.