JP2930511B2 - Aqueous polyolefin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aqueous polyolefin composition, which is obtained by adding water under pressure to a polyolefin and a modified polyolefin, and then converting the aqueous phase to an aqueous polyolefin composition. It is about things.

[0002]

2. Description of the Related Art Modified polyolefin compositions in which polyolefins such as polypropylene, polyethylene and copolymers of propylene, ethylene and α-olefin are modified with unsaturated carboxylic acids or acid anhydrides, and acid modified by chlorinating them. In producing a chlorinated polyolefin, a solubility parameter (sp value) 7 cal ^1/2 cm
The use of polyalkylene oxide derivatives of ^-3/2 or ^{12 cal} 1/2 ^{cm -3/2} or less is place, compared with the case of alcohols, low molecular weight glycols, using other surface active ingredients, more The present inventors have found that an aqueous resin composition having excellent stability and excellent water resistance can be effectively prepared in a small amount, and have already filed a patent application (Japanese Patent Application No. 5-64874).

[0003] A phase inversion emulsification method has been used as a method for producing this aqueous resin composition, but the stirring efficiency is markedly increased due to an increase in resin melt viscosity due to a decrease in temperature when hot water is added and an increase in viscosity during phase transition. However, there has been a problem of lowering the yield and lowering the yield because the undispersed resin component remains in the aqueous solution. Furthermore,
Since the average particle diameter of the obtained aqueous resin composition is large, there is also a disadvantage that when used as a primer at the time of coating or as a binder of an aqueous ink, the surface properties of the coating film are reduced.

[0004]

SUMMARY OF THE INVENTION The present invention reduces the increase in the viscosity of the reaction solution in the aqueous resin process, thereby increasing the stirring efficiency and improving the yield, and at the same time, reducing the average particle size of the aqueous resin. As a result, the aging stability is improved and the large diameter 2
The purpose is to suppress the formation of secondary aggregates.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted various studies to achieve the above object, and have reached the present invention. That is, in the present invention, when the polyolefin and / or the modified polyolefin are converted to an aqueous solution, the raw material resin is melted.
Surfactant and / or alcohol and basic to molten resin
After adding and mixing the substances, add
These raw materials are combined with a surfactant and / or alcohol under heat.
Lumpur compound and a basic gradually water under pressure of the mixture melts absolute with stirring pressure 1.1Kg / cm ² ~101Kg / cm ² in the range of substances
To cause a phase transition, and the resin component, liquid water and
A water-soluble polyolefin composition, wherein a water-soluble polyolefin composition is prepared while coexisting with the same temperature range and the same pressurized range, and has a polyalkylene oxide structure and a solubility parameter (sp value) of 7 cal ^{1. / 2} cm
^-3/2 more than 12cal ^1/2 cm ^-3/2 0.001 the following materials
In making the polyolefin and / or the modified polyolefin contained as a constituent component in a proportion of not less than 50% by weight or more into an aqueous solution, the raw material resin is melted and an interface is formed with the molten resin.
Add and mix activator and / or alcohol and basic substance
After that, these under heating in the range of 100 ℃ or more and 300 ℃ or less
Raw resin and surfactant and / or alcohol and basic
Absolute pressure 1.1Kg / cm ² while stirring the mixture with the substance
~101Kg / cm ² in the range gradually phases dropwise under pressure of water
Cause the transfer of resin components, liquid water and other components.
A method for producing an aqueous polyolefin composition, characterized in that the aqueous polyolefin composition is made aqueous while coexisting in the same temperature range and the same pressurized range.Furthermore, in the method for producing the aqueous polyolefin composition, a substance having a polyalkylene oxide structure is described below. A method for producing an aqueous polyolefin composition using a polyoxyalkylene diol represented by the general formula [I], and an aqueous method using an aliphatic alcohol ethylene oxide propylene oxide adduct represented by the following general formula [II] A method for producing a polyolefin composition, a method for producing an aqueous polyolefin composition using an aliphatic amine ethylene oxide propylene oxide adduct represented by the following general formula [III], and a polyoxyethylene represented by the following general formula [IV] Surfactant with alkyl phenyl ether structure, general At least one of the substances represented by the formulas [I], [II] or [III] is used in combination with another substance having a polyoxyalkylene structure at a ratio of 1: 200 to 200: 1. This is a method for producing an aqueous polyolefin composition.

The general formula [I] HO-[(PO) _n / (EO) _m ] -H [I] where E; -CH ₂ CH _2- n, m; an integer of 0 or more and 100 or less, 4 ≦ n + m ≦ 100 / indicates a structure obtained by random copolymerization or block copolymerization. When either n or m is 0, a homopolymer is obtained. .

General formula [II] RO-[(PO) _m / (EO) _n ] -H [II] wherein R; a group consisting of an aliphatic hydrocarbon having 1 to 50 carbon atoms E; -CH ₂ CH _2- n, m; an integer of 0 or more and 50 or less, 2 ≦ n + m ≦ 100 / indicates a structure obtained by random copolymerization or block copolymerization, and when either n or m is 0, it indicates a homopolymer. .

The general formula [III] However R; group consisting of aliphatic hydrocarbons having 1 to 50 carbon atoms E; -CH ₂ CH ₂ - n, m; an integer of 0 or more and 50 or less, 2 ≦ n + m ≦ 100 l, k; an integer of 0 or more and 50 or less, 2 ≦ l + k ≦ 100 / indicates a structure obtained by random copolymerization or block copolymerization, when either n or m is 0, or l,
When either k is 0, it indicates a homopolymer.

The general formula [IV] Where R is a lower alkyl group X; a hydrogen atom or a lower alkyl group, or a nonionic or anionic hydrophilic group n; an integer from 0 to 50 Y; a hydrogen atom, or —CH ₂ —O—CH ₂ —CH ＝ CH
₂ Z; hydrogen atom or -CH = CH-CH ₃ provided that Y and Z do not have a double bond at the same time

Hereinafter, the present invention will be described in detail. As the polyolefin used in the present invention, a homopolymer of ethylene or propylene, or ethylene or propylene and other comonomers such as butene-1, pentene-1,
Random copolymers or block copolymers with α-olefin comonomers having 2 or more carbon atoms, preferably 2 to 6, such as hexene-1, heptene-1, octene-1, or copolymers of two or more of these comonomers Is used. The average molecular weight of the polyolefin is usually from 2000 to 100,000.
A material obtained by a known method may be used, but a material once synthesized to a high molecular weight and degraded by radicals, oxygen or heat is also used.

The modified polyolefin is a polyolefin obtained by chlorinating the above polyolefin by a known method, or a polyolefin modified by grafting with an α, β-unsaturated carboxylic acid or an acid anhydride thereof. Further, a modified polyolefin modified by a combination of chlorination and acid modification is also used. Further, a polyolefin resin which has been subjected to aqueous modification by reacting a reactive surfactant with the above-mentioned polyolefin-based resin with a radical reaction initiator is also used as a water-based raw material.

Α, used for modification of polyolefin
Examples of β-unsaturated carboxylic acids or acid anhydrides thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid,
Allyl succinic acid, mesaconic acid, aconitic acid, and acid anhydrides thereof, and the like. The amount of graft copolymerizing the α, β-unsaturated carboxylic acid or anhydride thereof is 1 to
20% by weight is preferable, and when it is 1% by weight or less, stability when dispersed in water is deteriorated, and when it is 20% by weight or more, graft efficiency is deteriorated, which is uneconomical. Particularly preferably, 2 to
15% by weight.

The number average molecular weight of a resin obtained by graft copolymerizing an α, β-unsaturated carboxylic acid or an acid anhydride thereof is as follows:
3000 to 40,000 is preferable, and if it is 3000 or less, the cohesive strength is insufficient and the adhesion to the polyolefin resin is deteriorated,
If it is more than 40,000, the operability when dispersing in water becomes poor, which is not preferable. In order to make the molecular weight fall within this range, it is possible to select the molecular weight of the raw material and the conditions for performing the graft reaction, and it is also possible to perform the graft reaction after the molecular weight of the raw material is reduced. In addition,
The number average molecular weight can be measured by GPC (gel permeation chromatography).

The polyalkylene oxide structure used in the present invention has a solubility parameter (sp value) of 7
cal ^1/2 cm ^-3/2 or more ^12cal 1/2 cm
^As a surfactant component having a content of ^−3/2 or less , general formula [I],
[II], [III], polyoxyethylene diol, polyoxypropylene diol, polyoxytetraethylene glycol, copolymers of ethylene oxide and propylene oxide, polyoxyethylene polyoxypropylene block polymers, including the compounds of [IV], Aliphatic alcohol polyalkylene oxide adduct (polyoxyethylene aliphatic alkyl ether, etc.), secondary alcohol polyalkylene oxide adduct (polyoxyethylene secondary alcohol ether, etc.), alkylamine polyalkylene oxide adduct, alkylamide polyalkylene Oxide adduct, polyoxyalkylene alkyl phenyl ether (polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether, etc.), polio Sialkylene sterol ether, polyoxyalkylene lanolin derivative, alkylene oxide derivative of alkylphenol formalin condensate, polyoxyalkylene glycerin fatty acid ester (polyoxyethylene glycerin fatty acid ester, etc.), polyoxyalkylene sorbitol fatty acid ester (polyoxyethylene sorbitol fatty acid ester, etc.) ), Polyoxyalkylene glycol fatty acid ester (polyoxyethylene fatty acid ester, etc.), polyoxyalkylene fatty acid amide (polyoxyethylene fatty acid amide), polyoxyalkylene alkylamine (polyoxyethylene alkylamine, ethylene oxide propylene oxide of alkylalkanolamine) Polymer adduct) and the like. A substance having a polyalkylene oxide structure refers to an oligomer or a chemical structure composed of a polymer formed by homopolymerization or copolymerization (block copolymerization, random copolymerization, graft copolymerization, etc.) of an alkylene oxide such as ethylene oxide or propylene oxide. Substance.

The average molecular weight is from 200 to 5,000, preferably from 300 to 3,000. When the molecular weight is 200 or less, the dispersing performance is low and no remarkable effect is exhibited. Also the molecular weight
If it is more than 5000, the resin dispersing ability decreases. In addition, these
You may use in combination of types or more. The surfactant is used in an amount of 0.001 part to 50 parts, preferably 0.5 part to 20 parts, per 100 parts of the aqueous resin material.

The solubility parameter was calculated from the chemical composition of each substance by the method of Fedors et al.

Surfactants which can be used in combination with the above-mentioned surfactant include a reactive surfactant and a non-reactive surfactant.

The reactive surfactant may be one generally used as a reactive surfactant or a reactive emulsifier, but one having an alkylphenyl group as a hydrophobic group and a polyoxyethylene group as a nonionic hydrophilic group. Is preferred. For example, alkyl propenyl phenol polyethylene oxide adducts, alkyl dipropenyl phenol polyethylene oxide adducts, and salts of sulfates thereof as disclosed in JP-A-4-53802 and JP-A-4-50204 are used.

Among them, alkylpropenylphenol ethylene oxide 20 mol adduct, 30 mol adduct, and
Preference is given to ammonium sulfate salts of 50 mol adduct, 10 mol adduct of alkylpropenylphenol polyethylene oxide and ammonium sulfate salts of 20 mol adduct. Also, 1-alkylphenoxy-3-
The (2-propenyl) oxypropan-2-ol ethylene oxide adduct or a sulfate thereof is excellent in resin dispersibility, and further preferably has high polymerizability due to having an α, β-unsaturated double bond. These reactive surfactants can be reacted with an aqueous resin material by a radical reaction initiator by a known method and immobilized on the resin.

The amount of the reactive surfactant to be used is 0.0 to 100 parts of the modified polyolefin which is the aqueous resin material.
The amount is from 01 to 50 parts, preferably from 0.001 to 30 parts.
The amount used can be appropriately changed depending on the amount of addition of a non-reactive surfactant, which is another hydrophilic component. When a reactive surfactant is used, a reaction initiator is added.
This reactive surfactant may be reacted in advance with the aqueous material, or may be added during the aqueous process. Known reaction initiators can be used.

Examples of the non-reactive surfactant include nonionic surfactants such as propylene glycol ester, sucrose ester, sorbitan alkyl ester, sorbitan fatty acid ester, polyglycerin ester, fatty acid alkanolamide, fatty acid monoglyceride, and alkylamine oxide; Sulfate, alkyl phenol sulfonate, carboxylate other than sulfosuccinate and the like, and anionic surfactants that can also include phosphates such as alkyl betaine,
Amphoteric surfactants such as alkylimidazolines and the like and mixtures of two or more thereof can be used.

The amount of the non-reactive surfactant to be used is 0.0001 to 100 parts, preferably 0.0001 to 20 parts, based on 100 parts of the modified polyolefin which is a water-based raw material resin. When a surfactant that does not wait for a polyoxyalkylene structure is used in combination, the total amount of the
It is desirable that the amount be 0.001 part to 50 parts, more preferably 0.001 part to 10 parts, per part.

In addition, in the aqueous process of acid-modified polyolefin or the like, the dispersibility of the resin in water can be controlled by adding a basic substance to neutralize the resin and ionizing the hydrophilic group. Furthermore, the pH of the aqueous solution can be adjusted by adding a basic substance. These basic substances can be added during the melting and stirring of the resin, or can be added to the aqueous solution.

The basic substance includes sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate, potassium carbonate, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine,
Octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-
Examples thereof include 2-methyl-1-propanol and morpholine. The amount of the basic substance to be used varies depending on the aqueous base resin, but is 0.01 to 25 parts.

The pressure and the temperature of the reaction system are each absolute pressure 1.1.
kg / cm ² ~ 101kg / cm ² , 100 ℃ ~ 300 ℃
Preferably, the absolute pressure is 1.5 kg / cm ^{2 to} 51 kg / cm ² , and the temperature is 1
It is in the range of 10 ° C. to 250 ° C., and is appropriately set according to the softening temperature of the aqueous resin material used, the cloud point of the surfactant, and the like. The higher the temperature, the lower the melt viscosity of the resin, which is preferable. However, the temperature must be lower than the decomposition temperature of the water-based raw material resin, surfactant and the like.

When the aqueous solution is formed by using such a method, the viscosity of the raw material resin is reduced as compared with the conventional phase inversion method under the atmospheric pressure, so that the stirring efficiency is increased and the yield is remarkably improved. Furthermore,
Since an aqueous resin having an average particle size smaller than that of the conventional method can be obtained, the formation of secondary aggregated particles is suppressed and the storage stability is improved.

[0027]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Prototype example) In a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, a propylene-α-olefin copolymer (75 mol% of propylene component,
Ethylene component 20 mol%, 1-butene component 5 mol%, number average molecular weight 25,000) 300 g of toluene was heated and dissolved in 700 g of toluene, and then 13 g of maleic anhydride and radical generator were added while stirring while maintaining the system temperature at 115 ° C. 12 g of di-t-butyl peroxide was added dropwise over 2 hours, followed by aging for 3 hours. After the reaction, the reaction product was cooled to room temperature, and the reaction product was poured into 20 L of acetone and purified. The graft copolymer of maleic anhydride having a graft amount of 2.1% by weight (average molecular weight 1
8500).

In the measurement of the average molecular weight, Tosoh HP
A column TSK-GEL was attached to LC-8020, the sample was dissolved in THF (tetrahydrofuran), measured at 40 ° C., and the molecular weight was determined from a calibration curve prepared using a polystyrene standard sample.

Example 1 100 parts of the modified polyolefin resin obtained in the prototype example was charged into a 1.5 L autoclave equipped with a stirrer, a thermometer, a pressure gauge, and a pressurized metering pump, and heated and melted at 130 ° C. Thereafter, 10 parts of morpholine was added as a basic substance while stirring, and 20 parts of polyethylene oxide (average molecular weight: 1000) was further added as a surfactant. After stirring until uniform, 400 parts of warm water at about 90 ° C. was added successively under a pressure of 1.6 kg / cm ² to obtain an aqueous product by a phase inversion method. After adjusting the pH of the aqueous solution to 6 to 8, the aggregate having a particle size of 100 μm or more was removed by filtration to obtain an aqueous polyolefin composition.

The aggregate was dried at 130 ° C. for 24 hours, weighed, and the yield was determined. The average particle size of the hydrate was measured with a laser diffraction particle size analyzer. Further, the aqueous solution was allowed to stand at 40 ° C. for 2 weeks, and the production status of the seeds, phase separation, and the like were visually observed to obtain an index of stability over time.

Example 2 The surface active component was replaced with 10 parts of polypropylene oxide (average molecular weight 400) and 5 parts of polyoxyethylene nonyl phenyl ether (Nonion NS-208.5, manufactured by NOF Corporation). The same operation as in Example 1 was performed to obtain an aqueous product. The yield, the average particle size of the aqueous hydrate, and the stability over time were measured in the same manner as in Example-1.

(Comparative Example 1) 100 parts of the modified polyolefin resin obtained in the prototype example was charged into a 1.5 L autoclave equipped with a stirrer, a thermometer, a pressure gauge and a pressure metering pump, and was heated and melted at 130 ° C. Thereafter, 10 parts of morpholine as a basic substance, 10 parts of polypropylene oxide (average molecular weight 400) as a surfactant, and polyoxyethylene nonylphenyl ether (Nonion NS-2 manufactured by NOF Corporation)
08.5) 5 parts and further 400 parts of hot water at about 90 ° C. were added.
The mixture was stirred under a pressure of 1.6 kg / cm ² for 1 hour, and an aqueous product was obtained by a forced emulsification method. The yield, the average particle size of the aqueous hydrate, and the stability over time were measured in the same manner as in Example-1.

Comparative Example 2 100 parts of the modified polyolefin resin obtained in the prototype example was charged into a reactor equipped with a stirrer, a thermometer, a cooling tube, and a dropping funnel, heated and melted at 120 ° C., and then stirred. 10 parts of morpholine is added as a basic substance, and 10 parts of polypropylene oxide (average molecular weight: 400) as a surfactant, and polyoxyethylene nonylphenyl ether (Nonion NS-208.
5) 5 parts were added. Stir until uniform, then add water 4
An aqueous product was obtained by the phase inversion method by adding 00 parts little by little.
Yield, average particle size of aqueous compound in the same operation as in Example-1,
The stability over time was measured.

The yields of Examples 1 and 2 and Comparative Examples 1 and 2,
Table 1 shows the measurement results of the average particle size and the stability over time of the aqueous solution.

[0036]

[Table 1]

[0037]

By using the method for producing an aqueous polyolefin composition according to the present invention, the increase in the viscosity of the reaction solution in the aqueous process is reduced, the stirring efficiency is increased, and the yield is improved as compared with the conventional method. The average particle size of the aqueous resin can be reduced. In addition, by reducing the particle size of the aqueous compound, secondary aggregation is less likely to occur, and there is an effect of suppressing the occurrence of lumps and improving the stability over time. Therefore, when the aqueous polyolefin composition prepared by using the production method of the present invention is used as a primer or a binder for aqueous ink at the time of coating, the surface properties of the coating film can be improved.

Claims (7)

(57) [Claims] (1) In converting a polyolefin and / or a modified polyolefin into an aqueous solution, the raw material resin is melted.
Surfactant and / or alcohol and basic to molten resin
After adding and mixing the substances, add
Under heat, these raw materials are combined with a surfactant and / or alcohol
Absolute pressure while stirring the molten mixture of
Water is gradually applied under pressure in the range of 1.1 kg / cm ^{2 to} 101 kg / cm ²
Drop to cause phase transition, resin component, liquid water and other
Wherein the components are made aqueous while coexisting in the same temperature range and the same pressure range . 2. A having a polyalkylene oxide structure solubility parameter (sp value) 7cal ^1/2 cm ^-3/2 or 12c
The al ^1/2 cm ^-3/2 following materials Upon to aqueous the polyolefin and / or modified polyolefin comprising as a constituent in a proportion of less than 50 wt% 0.001 wt% or more, the
The raw material resin is melted and a surfactant and / or
After adding and mixing alcohols and basic substances,
Interface with these raw materials under heating in the range of not less than 300 ° C
Mixed solution of activator and / or alcohol and basic substance
While stirring the melt, water is gradually dropped under a pressure in the range of absolute pressure of 1.1 kg / cm ^{2 to} 101 kg / cm ² to cause a phase transition,
Add resin component, liquid water and other components in the same temperature range and
A method for producing an aqueous polyolefin composition, wherein the aqueous polyolefin composition is made aqueous while coexisting in a pressure range. 3. The method for producing an aqueous polyolefin composition according to claim 2, wherein a polyoxyalkylene diol represented by the following general formula [I] is used as the substance having a polyalkylene oxide structure. General formula [I] HO-[(PO) _n / (EO) _m ] -H [I] where E; -CH ₂ CH _2- n, m; an integer of 0 or more and 100 or less, 4 ≦ n + m ≦ 100 / indicates a structure obtained by random copolymerization or block copolymerization. When either n or m is 0, a homopolymer is obtained. . 4. A method for producing an aqueous polyolefin composition using an aliphatic alcohol ethylene oxide propylene oxide adduct represented by the following general formula [II] as a substance having a polyalkylene oxide structure according to claim 2. General formula [II] RO-[(PO) _m / (EO) _n ] -H [II] wherein R; a group consisting of an aliphatic hydrocarbon having 1 to 50 carbon atoms E; —CH ₂ CH ₂ — n, m; an integer of 0 or more and 50 or less, 2 ≦ n + m ≦ 100 / indicates a structure obtained by random copolymerization or block copolymerization, and when either n or m is 0, it indicates a homopolymer. . 5. A method for producing an aqueous polyolefin composition using an aliphatic amine ethylene oxide propylene oxide adduct represented by the following general formula [III] as a substance having a polyalkylene oxide structure according to claim 2. General formula [III] However R; group consisting of aliphatic hydrocarbons having 1 to 50 carbon atoms E; -CH ₂ CH ₂ - n, m; an integer of 0 or more and 50 or less, 2 ≦ n + m ≦ 100 l, k; an integer of 0 or more and 50 or less, 2 ≦ l + k ≦ 100 / indicates a structure obtained by random copolymerization or block copolymerization, when either n or m is 0, or l,
When either k is 0, it indicates a homopolymer. 6. The method according to claim 2, wherein the surface active component having a polyoxyethylene alkylphenyl ether structure represented by the following general formula [IV]: An aqueous polyolefin, characterized in that at least one of the substances represented by I], [II] or [III] is used in combination with another substance having a polyoxyalkylene structure at a ratio of 1: 200 to 200: 1. A method for producing the composition. General formula [IV] Where R is a lower alkyl group X; a hydrogen atom or a lower alkyl group, or a nonionic or anionic hydrophilic group n; an integer from 0 to 50 Y; a hydrogen atom, or —CH ₂ —O—CH ₂ —CH ＝ CH
₂ Z; hydrogen atom or -CH = CH-CH ₃ provided that Y and Z do not have a double bond at the same time 7. An aqueous polyolefin composition obtained by the production method according to claim 1.