JP2804978B2 - Modifier for polymer, method for producing the same, and method for modifying polymer using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a modifying agent and a modifying method. More specifically, a polymer modifier comprising a sulfate (salt) having excellent storage stability by containing a specific polymerization inhibitor in a specific amount, a method for producing the same, and a polymer modification using the same About the method.

[0002]

2. Description of the Related Art Conventionally, ethylenically unsaturated monomers (hereinafter, referred to as a monomer) such as polymers such as (meth) acrylonitrile, styrene, butadiene, (meth) acrylic acid or a salt or ester thereof, vinylidene chloride, and vinyl chloride. A method of using a sulfate (salt) represented by the general formula (1) for the purpose of modifying a polymer of the formula (1) is known (JP-A-60-170611, JP-A-62-349).
47 gazette). General formula (Wherein R is a hydrogen atom or a methyl group, A is an alkylene group, M is a monovalent or divalent cation, and represents an oxyalkylene group as OA. N is an integer of 2 or more, m is 1 or 2 And represents the valency of the cation.)

[0003]

However, these modifiers have poor storage stability and need to be stored at a low temperature. In addition, there is a problem that even when stored at a low temperature, a polymer is partially produced as a by-product and the effect of modifying the polymer is reduced.

[0004]

Means for Solving the Problems As a result of intensive studies for solving these problems, the present inventors have found that a specific amount of a specific polymerization inhibitor is contained so that a sulfate ester having excellent storage stability can be obtained. Alternatively, a copolymerizable modifier for a polymer comprising a salt and a method for modifying the polymer have been found, and the present invention has been accomplished. That is, the present invention provides a phenolic thread compound (B1) and / or an amine compound (B
2) with 50 to 3,000 ppm, and copper ion (C) 0.1.
A copolymerizable modifier for a polymer consisting of the sulfate (salt) (A) represented by the general formula (1) containing 01 to 20 ppm; a method for producing the same; and a method for producing a polymer of an ethylenically unsaturated monomer. This is a method for modifying a polymer using the copolymerizable modifier in a method of modifying the copolymer by copolymerizing an anionic monomer during production. General formula (Wherein, R is a hydrogen atom or a methyl group, A is an alkylene group, M is a monovalent or divalent cation, and (OA) _n
Represents a polyoxyalkylene group. n is a number from 2 to 30,
m is 1 or 2 and represents the valence of a cation. )

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the sulfate ester or its salt (A) of the present invention, the alkylene group represented by A in the general formula (1) is, for example, an alkylene group having 2 to 4 carbon atoms (ethylene group, propylene group). Group, butylene group). These alkylene groups together with oxygen form an oxyalkylene group. The oxyalkylene groups may be the same or different, and their bonding mode may be block-like or random. Preferred is an oxypropylene group, or a combination of an oxyethylene group and an oxypropylene group. It is particularly preferred that the number of oxypropylene groups in the polyoxyalkylene chain is 2
These are included. Examples of M include hydrogen, alkali metals (such as lithium, sodium, and potassium), alkaline earth metals (such as calcium and magnesium), ammonium, and organic amine cations (such as alkanolamines and lower alkylamines). Of these, alkali metals (sodium, lithium, potassium) and ammonium are preferred. n is usually 2 to 30,
Preferably, it is 3 to 15. When n is 1, compatibility with the monomer to be polymerized is poor, and copolymerization becomes difficult. When n exceeds 30, the copolymerizability of the monomer to be polymerized becomes poor.

Examples of the sulfate (salt) represented by the general formula (1) include compounds represented by the following general formulas (2) and (3). General formula General formula In the general formula (3), the oxypropylene group and the oxyethylene group may be random or block. Among these, preferred are those represented by the following general formula (4).

As a method for producing a sulfate (salt) represented by the general formula (1), for example, (1) an alkylene oxide adduct of (meth) acrylic acid is converted into a sulfate and, if necessary, a salt with a sulfating agent. Method (2) A method in which polyalkylene glycol monosulfate (salt) and (meth) acrylic acid are esterified to form a salt if necessary. The method (1) includes a method of adding an alkylene oxide to (meth) acrylic acid, hydroxyethyl or hydroxypropyl (meth) acrylate, and a method of dehydrating and condensing a polyalkylene glycol with (meth) acrylic acid. Examples of the sulfating agent for producing a sulfate ester include fuming sulfuric acid, sulfuric acid, chlorosulfuric acid, and sulfamic acid. Examples of the method for forming a salt include a method of neutralizing with a hydroxide of an alkali metal or an alkaline earth metal, aqueous ammonia, an organic amine, or the like. Furthermore, there is a method of adding urea for the purpose of preventing coloration during sulfation.

[0008] In the case of the sulfate salt of the present invention,
In the case of large-scale production, when a salt obtained by sulfating with fuming sulfuric acid, sulfuric acid or chlorosulfuric acid as a sulfating agent is further neutralized with an alkali to form a salt, the sulfate may be hydrolyzed. That is, in the step of adding the sulfate ester to the alkali, the pH is high, so that it is easily hydrolyzed to (meth) acrylic acid and polyalkylene glycol monosulfate. Conversely, in the step of adding an alkali to the sulfate, the initial pH is low, so that hydrolysis to the alkali salt of polyalkylene glycol (meth) acrylate and sulfuric acid is likely to occur. On the other hand, when sulfamic acid is used as the sulfating agent, an ammonium salt is already formed, so that further neutralization is not required, which is preferable. This may be further subjected to salt exchange with an alkali metal or alkaline earth metal hydroxide.

In the case of a sulfation reaction, to prevent polymerization,
Phenol compound (B1), amine compound (B2)
And copper ion (C) must be added in advance. As the amount of the polymerization inhibitor at the time of the sulfation reaction, there is a method in which an amount necessary for preventing the polymerization of the side reaction or an excessive amount is added, and the excess polymerization inhibitor is removed after the sulfation reaction. Examples of the removing method include a method using an adsorbent and a method using extraction.

In the present invention, as the phenolic polymerization inhibitor (B1), hydroquinone monomethyl ether, hydroquinone, 2,6-di-tert-butyl-
4-methylphenol, 2,4-dimethyl 6-tert-butyl-phenol, pyrogallol and the like. Examples of the amine polymerization inhibitor (B2) include phenothiazine and diphenylamine. Preferred among these polymerization inhibitors are hydroquinone monomethyl ether and phenothiazine. The amount of polymerization inhibitor is
Usually 50 to 3,000 pp for the modifier of the present invention
m, preferably 300 to 1,500 ppm. 50
If the amount is less than 3 ppm, a polymer is by-produced over time,
When the content exceeds 0 ppm, polymerization inhibition occurs when the monomer is used as a modifier when producing a polymer.

In the present invention, copper compounds forming copper ions (C) include cupric chloride, copper sulfate, cupric hydroxide and the like. The copper compound may form a salt or a complex with another substance in the modifier. The content of copper ion (C) is usually 0.0
It is 1 to 20 ppm, preferably 0.1 to 10 ppm, particularly preferably 0.1 to 5 ppm. When the copper content is less than 0.01 ppm, a polymer is by-produced over time. Even when it exceeds 20 ppm, a polymer is by-produced,
Further, when used as a modifier in the production of a polymer using a monomer, polymerization is inhibited. In the present invention, when only one of the phenol-based polymerization inhibitor and / or the amine-based polymerization inhibitor and copper ion is used, a polymer is by-produced over time.

In the present invention, a buffer (D) can be further used to further improve the storage stability. Examples of the buffer include salts of organic acids (such as citric acid, tartaric acid, malic acid, lactic acid, and acetic acid) and salts of phosphoric acid (such as sodium, potassium, and ammonium). This buffer may be used alone or in combination. Among these, preferred are organic acids and salts thereof, and particularly preferred are citric acid and citrates (sodium hydrogen, sodium citrate, etc.). The content of the buffer in the modifier of the present invention is usually 50 to 5,000 ppm, preferably 2,500 to 3,000 ppm.

The modifier of the present invention is used for modifying a polymer, particularly a polymer of an ethylenically unsaturated monomer, and the polymer may be a synthetic resin, a synthetic rubber, a synthetic fiber, a synthetic fiber, Used as resin emulsion. For example, the following ethylenically unsaturated monomers can be mentioned. (A) Nitrile group-containing monomer (meth) acrylonitrile (b) Ester of unsaturated carboxylic acid [(meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, etc.] C1-20 alkyl (methyl, ethyl) , Butyl,
(Meth) acrylate; di (meth) acrylate of glycol (ethylene glycol, 1,4-butanediol, polypropylene glycol, etc.); carbon number 1 of maleic acid, fumaric acid, itaconic acid
(C) Amide of unsaturated carboxylic acid (meth) acrylamide (d) Halogen-containing monomer Vinyl chloride, vinylidene chloride, chloroprene, etc. (e) Aromatic vinyl monomer Styrene, α-methylstyrene, vinyltoluene, etc. (f) Aliphatic hydrocarbon monomers, ethylene, propylene, butadiene, isoprene, etc. (g) vinyl ester or (meth) allyl ester vinyl acetate, vinyl propionate, divinyl phthalate, allyl acetate, etc. (H) unsaturated carboxylic acids and salts thereof (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and salts thereof

The amount of the modifier used in the present invention depends on the type of the polymer,
Various changes can be made depending on the composition, purpose, required performance and the like of the monomer. When producing a hydrophobic polymer for the purpose of antistatic properties, dyeing properties, etc., the modifier of the present invention usually contains 0.1 to 10% by weight in the polymer, preferably,
The content is preferably 0.2 to 5% by weight. 0.1
If the amount is less than% by weight, the antistatic effect and the effect of improving dyeability are small. If the amount is more than 10% by weight, the affinity for water is often too strong to be disadvantageous. When used for the purpose of improving the water resistance and adhesiveness of the dried coating film of the synthetic resin emulsion, 0.1 to 20% by weight, preferably 0.5% by weight.
~ 5% by weight. If it is less than 0.1% by weight, the storage stability of the synthetic resin emulsion will be poor. On the other hand, if it exceeds 20% by weight, the water resistance and adhesiveness of the dried coating film of the synthetic resin emulsion are reduced.

The modification of the polymer with the modifier of the present invention can be carried out by various methods. The polymerization method may be any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The polymerization may be any of block polymerization, random polymerization, and graft polymerization. Further, it may be polymerized on the surface of a foam molded product, fiber, film, cast product or the like.

The modifier of the present invention is particularly useful as a reactive emulsifier used in the emulsion polymerization of monomers. Such an emulsifier can be used in various ways. For example, in the emulsion polymerization method, it can be carried out by using the modifier of the present invention instead of a usual emulsifier.

As a method for initiating polymerization, an electron beam,
A method by irradiating γ rays or ultraviolet rays, a method of starting by heating, a method of using a polymerization initiator, and the like can be used. In the method using an initiator, the initiator may be a persulfate (ammonium persulfate, potassium persulfate, etc.); a peroxy compound (benzoyl peroxide, lauroyl peroxide, hydrogen peroxide, etc.); an azo-based initiator (azobis Initiators such as isobutyronitrile); redox initiators (sulfite and peroxy compound, hydrogen peroxide and iron (divalent), etc.) can be used.

In the case of solution polymerization, solvents such as dimethylformamide, dimethylacetamide and dimethylsulfoxide are used. In the case of emulsion polymerization or suspension polymerization, a mixed solvent of water and a water-soluble solvent (methanol, isopropyl alcohol, acetone, etc.) can be used.

In the above-mentioned polymerization method, a polymerization regulator such as various mercaptans (such as dodecyl mercaptan) and a dispersant such as partially saponified polyvinyl alcohol can be used as required in the polymerization. In the case of emulsion polymerization, other emulsifiers can be used, for example, anionic surfactants (such as sodium dodecylbenzenesulfonate and sodium lauryl sulfate) and nonionic surfactants (such as polyoxyethylene alkylphenyl ether and polyoxyethylene). Ethylene alkyl ether)
Can be used. The amount of these emulsifiers is limited due to performance such as water resistance of the dried coating.

In the above various polymerization methods, the polymerization temperature varies depending on the polymerization method and the type of the monomer to be copolymerized, but is usually -5 to 150 ° C.

In the above various polymerization methods, in addition to the modifier of the present invention, other anionic monomers [(meth) acrylic acid, sulfopropyl (meth) acrylate, sulfopropyl (meth) acrylamide, styrene sulfone Acid salt, etc.] can also be used in combination. When used in combination, the amount of the modifier of the present invention is usually at least 20% by weight, preferably at least 50% by weight, based on the total weight of the modifier of the present invention and other anionic monomers.

The modifier of the present invention has higher performance (polymerization degree, antistatic property, dyeing property, etc.) in that the polymerization rate of the monomer is higher than that of a known anionic monomer modifier. The resulting polymer emulsion has excellent mechanical stability and chemical stability, has low foaming properties, and the dried coating film obtained from the polymer emulsion is excellent. Water resistance, having adhesive properties, does not impair the transparency of the polymer film, can impart hydrophilicity to the polymer, dust on the surface of the polymer film,
Dirt such as oil and dirt is hard to adhere, and even if it adheres, it can be easily removed.When taking out the polymer from the emulsion, performance and effects such as giving a polymer emulsion with almost no emulsifier flowing out into wastewater Have.

The polymer modified according to the present invention is useful as a synthetic resin, a synthetic fiber, a fiber treating agent, a paper processing agent, a hair spray resin, and the like. Emulsions of these polymers can be used for the production of compositions for adhesion, coating, impregnation and dispersion, etc., and can be used for water-based paints, water-based adhesives, resins for paper processing, resins for fiber processing (pastes and nonwoven fabrics). Binder, etc.), fiber modifier, resin emulsion for floor polish, resin for soil erosion prevention, admixture for concrete and mortar. Further, it can be used for manufacturing synthetic resins such as polyvinyl chloride and ABS resin, synthetic rubber, synthetic fibers and the like.

[0024]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the analysis method and the evaluation method are as follows.

<Copper ion content> Using an atomic absorption spectrophotometer (model: HITACHI 180-80),
The absorbance at 4.8 nm was measured, and the copper ion content was determined from the calibration curve.

<Hydroquinone monomethyl ether content> The absorbance at 420 nm was measured using a spectrophotometer (HITACHI U-1000), and the hydroquinone monomethyl ether content was determined from a calibration curve.

<Amount of polymer by-product during synthesis> HPLC analysis was performed, and the content (%) of polymer by-produced was determined from the peak area of the chart. (HPLC conditions) Model: LC-10AD (manufactured by Shimadzu Corporation) Column: ShodexOHpakSB-802.5 (manufactured by Showa Denko KK) Mobile phase: methanol / high-purity ion-exchanged water = 57/43
(Volume ratio) Flow rate: 0.6 ml / min Sample concentration: 0.9% Injection volume: 10 μl Detector: differential refractometer

<Amount of polymer by-product during storage> The polymer was stored in a thermostat at 50 ° C. for 3 months, and the amount of the polymer by-product was measured by HPLC. The method for obtaining the amount of the polymer and the measurement conditions are the same as the amount of the polymer by-product during the synthesis.

<Polymerization Inhibition of Monomer> Example 1 described later
1, emulsion polymerization was carried out in the same manner except that the modifiers of Examples 1 to 9 and Comparative Examples 1 to 6 in Table 1 were used instead of (Modifier X1) to prepare a polymer emulsion, 1.5 g of the obtained polymer emulsion was weighed, and at 130 ° C.
The weight after drying for 5 hours was measured, and the polymerization conversion of the monomer was determined from the percentage (%) of the evaporation residue with respect to the theoretical solid content when 100% polymerization was performed. Further, the polymerization inhibition property of the monomer was determined based on the value according to the following criteria. ：: no polymerization inhibition; polymerization conversion rate: 97% or more Δ: slight polymerization inhibition; polymerization conversion rate: 90% to 97
%: Polymerization inhibition large; polymerization conversion = less than 90%

<Emulsion polymerization conversion> 1.5 g of the polymer emulsion obtained in Example 10 and Comparative Example 7 described below were weighed, and the weight after drying at 130 ° C. for 1.5 hours was measured.
The polymerization conversion of the monomer was determined from the percentage (%) of the evaporation residue with respect to the theoretical solid content when the polymerization was performed at 00%.

<Agglomerate content> The resulting mixture was filtered through a 150-mesh wire gauze, and the residue was washed with water and dried at 130 ° C for 5 hours.

<Mechanical Stability of Emulsion> 22 g of the polymer emulsion was placed in a beaker and mixed with a homomixer.
The mixture was stirred at 10,000 rpm for 30 minutes, and the formed solid was filtered off through a 150-mesh wire net, washed with cold water, and then washed at 130 ° C.
For 5 hours. The weight of the dried product was expressed in% with respect to the weight of the solid in the collected emulsion.

<Chemical stability of emulsion> 50 ml of a polymer emulsion diluted with water to a solid content of 0.5%
Was expressed by the volume (ml) of 1/10 N CaCl ₂ required for coagulation and separation.

<Foaming property of emulsion> 100 ml of 30 ml of a polymer emulsion diluted with water to a solid content of 3% was used.
And vigorously shake it 10 times, and expressed as the foam amount (ml) after 5 minutes.

<Water resistance of the film> The polymer emulsion was spread on a slide glass, and further heated at 60 ° C for 8 hours for 2 hours.
After drying at 0 ° C. for 24 hours, a film having a thickness of 0.2 mm was prepared. The water resistance of this film was determined according to JISK-68.
Tested according to 28 drop test methods and expressed in hours.

<Adhesiveness of film> A cellophane adhesive tape was applied to the film prepared by the above method,
The adhesive strength between the film and the cellophane pressure-sensitive adhesive tape was measured by an 80 ° peel test, and the result was expressed in g / cm.

<COD in Emulsion Waste Liquid> The polymer emulsion was frozen and destroyed by freezing at -10 ° C. for 24 hours, and after melting at 30 ° C., the polymer was separated by filtration. COD of filtrate
Was measured in accordance with JIS K0102-1971, and ppm
Indicated by

Production Example 1 In a 5 L glass flask, 608 g of polyoxypropylene (n = 9) glycol monomethacrylate, 1.05 g of hydroquinone monomethyl ether, and 304 g of ethylene dichloride were charged and uniformly dissolved. -3 to
At 5 ° C., 139.8 g (1.2 mol) of chlorosulfuric acid was gradually added dropwise over 10 hours while removing hydrochloric acid.
% Of methacryloyloxypolyoxypropylene (n =
9) 681 g of sulfate ester was obtained. Then, -3 to 5 ° C
Then, 430 g of a 20% aqueous sodium hydroxide solution was gradually charged and neutralized to obtain 703 g of sodium methacryloyloxypolyoxypropylene (n = 9) sulfate.
Its pH was 6.5. Then, Radiolite # 600 [manufactured by Showa Chemical Industry Co., Ltd.] 3 as a filter aid
Using 0 g, the precipitated sodium sulfate and sodium chloride were separated by filtration to obtain 1,303 g of a filtrate. Water 390 in the filtrate
g, and 1,2-dichloroethane was distilled off at 45 ° C. and 150 torr, and an aqueous solution 1 containing 668 g of methacryloyloxypolyoxypropylene (n = 9) sulfate sodium salt containing 1500 ppm of hydroquinone monomethyl ether was added. 336 g were obtained. This was designated as (Modifier Y1).

Preparation Example 2 In Preparation Example 1, 0.385 g of cupric chloride dihydrate (0.1% as copper) was used in place of hydroquinone monomethyl ether.
144g), and instead of Radiolite # 600, Kyoward 1000 [Kyowa Chemical Industry Co., Ltd.]
Methacryloyloxypolyoxypropylene (n = 9) containing 10 ppm of copper ions in the same manner as described above except that copper is adsorbed using 34 g of Kyoward 700SL [manufactured by Kyowa Chemical Industry Co., Ltd.] and 68 g of Kyoward 700SL. 1.) 265 g of an aqueous solution containing 632 g of sodium sulfate salt were obtained. This was designated as (Modifier Y2).

Production Example 3 608 g of polyoxypropylene (n = 9) glycol monomethacrylate and 0.385 g of cupric chloride dihydrate (0.1% as copper ions) were placed in a 5 L glass flask.
144 g), hydroquinone monomethyl ether 1.0
5 g and 6.1 g of urea were charged and uniformly dispersed. 126.1 g (1.3 mol) of sulfamic acid was charged and reacted at 90 ° C. for 10 hours to obtain 670 g of methacryloxypolyoxypropylene (n = 9) sulfate ammonium salt having a sulfation rate of 95%. Then cooled to 30 ° C,
705 g of dichloropropane was added and uniformly dissolved. Adsorbent (Kyoward 1000 (34g), Kyoward 70
After adsorption treatment using 0SL (68 g): manufactured by Kyowa Chemical Industry Co., Ltd., the mixture was filtered off. Copper ion content (per active ingredient)
1,300 g of a 2 ppm filtrate were obtained. Then 648 g of water
, And 1,2-dichloropropane was distilled off at 35 ° C. and 60 torr. Under the same conditions, sodium hydroxide 30
117.5 g of a 10% aqueous solution was added dropwise over 5 hours while distilling ammonia out of the system. Aqueous solution 1,29 containing 620 g of methacryloyloxypolyoxypropylene (n = 9) sulfate sodium salt containing 2 ppm of copper ion and 1,500 ppm of hydroquinone monomethyl ether
6 g were obtained. This was designated as (Modifier X1).

Production Example 4 In the same manner as in Production Example 3, except that 1.20 g of phenothiazine was used instead of hydroquinone monomethyl ether, a copper ion content of 3 ppm and phenothiazine 1,0 were used.
1,296 g of an aqueous solution containing 620 g of methacryloyloxypolyoxypropylene (n = 9) sulfate sodium salt containing 00 ppm was obtained. This was designated as (Modifier X2).

Production Example 5 In Production Example 3, oxypropylene 7 was used instead of polyoxypropylene (n = 9) glycol monomethacrylate.
In the same manner except that 580 g of a methacrylate of a 2 mol / oxyethylene random adduct was used, a copper ion content of 1 ppm, hydroquinone monomethyl ether 1,
1,280 g of an aqueous solution containing 600 g of the following methacryloyloxypolyoxyalkylene sulfate sodium salt containing 600 ppm was obtained. This was designated as (Modifier X3).

Production Example 6 In Production Example 3, oxypropylene 7 was used instead of polyoxypropylene (n = 9) glycol monomethacrylate.
Mol / oxyethylene 2 mol random adduct 580 g, except that copper ion content 1 ppm, hydroquinone monomethyl ether 1,0
1,280 g of an aqueous solution containing 595 g of the following acryloyloxypolyoxyalkylene sulfate sodium salt containing 00 ppm was obtained. This was designated as (Modifier X4). _{CH 2 = CH 2 -CO (OC} 3 H 6) 7 (OC 2 H 4) 2 OS0
₃ Na

Production Example 7 In the same manner as in Production Example 2 except that 1.05 g of hydroquinone monomethyl ether was used together with 0.385 g of cupric chloride dihydrate (0.144 g of copper), 10 ppm of copper ion and hydroquinone were used. Methyl ether 1,500
1,265 g of an aqueous solution containing 632 g of methacryloyloxypolyoxypropylene (n = 9) sulfate sodium salt containing ppm. This was designated as (Modifier X5).

Production Example 8 The method of Production Example 3 in which only hydroquinone monomethyl ether was added without prior addition of cupric chloride dihydrate and the mixture was subjected to a sulfation reaction at 90 ° C., containing 1,000 ppm of hydroquinone monomethyl ether. Methacrylyloxy polyoxypropylene (n = 9) sulfate sodium salt 6
1,290 g of an aqueous solution containing 25 g were obtained. This was designated as (Modifier Y3).

Examples 1 to 5 (Modifier X1) to (Modifier X) obtained in Production Examples 3 to 7
5) was used without any addition of a polymerization inhibitor. Examples 6 to 8 (Modifier Y1) and (Modifier Y) obtained in Production Examples 1 and 2
2) To each 100 g, cupric chloride dihydrate and hydroquinone monomethyl ether were further added so as to have the amounts shown in Table 1, and uniformly dissolved, and (Modifier X6) to (Modifier X)
8). Example 9 To 100 g of (Modifier Y2), hydroquinone monomethyl ether was further added at 1,000 ppm per active ingredient and trisodium citrate as a buffering agent at 3,000 ppm per active ingredient, and uniformly dissolved. (Modifier X
9).

Comparative Examples 1 to 3 (Modifier Y1), (Modifier Y2) and (Modifier Y3) were used as comparative examples without further addition. Comparative Examples 4 to 6 (Modifier Y1), (Modifier Y2), (Modifier X1) 10
0 g of cupric chloride dihydrate and hydroquinone monomethyl ether in the amounts shown in Table 1 (Modifier Y
4) to (Modifier Y6).

The copper ion content, hydroquinone monomethyl ether content, phenothiazine content, trisodium citrate content, the amount of polymer by-product during synthesis, the amount of polymer by-product during storage and the amounts of Examples 1 to 9 and Comparative Examples 1 to 6 Table 1 shows the evaluation results of the polymerizability with the monomer.

[0049]

[Table 1]

* MEHQ: Hydroquinone monomethyl ether ** PT: Phenothiazine *** SC: Trisodium citrate

Example 10 Under a nitrogen atmosphere, a glass mold was charged with 50 g of methyl methacrylate, 2 g of water obtained by removing the water content of (modifier X1) to 0.2%, and 0.1 g of lauroyl peroxide. Polymerization was performed for 4 hours to obtain a polymer having a thickness of 2 mm. After cooling, the polymer removed from the mold was a transparent glass-like resin plate having a polymerization conversion of 99.9%. The surface resistance of this resin plate was determined according to JIS K6911-19.
79 was measured by the method, the antistatic properties are 5 × 10 [Omega ¹¹ was good.

Example 11 117.5 g of ion-exchanged water was placed in a reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen inlet, a thermometer and a reflux condenser.
(Modifier X1) 1.6 g, sodium bicarbonate 0.08
g, ammonium persulfate 0.16 g, styrene 22 g and butyl acrylate 18 g, and stirred and emulsified,
After purging with nitrogen, polymerization was carried out at 75 ° C. for 30 minutes with stirring. Subsequently, 134.5 g of ion-exchanged water and (modifier X1) were added in an amount of 5.
An emulsion composed of 6 g, 0.28 g of sodium hydrogen carbonate, 0.56 g of ammonium persulfate, 77 g of styrene, and 63 g of butyl acrylate was added dropwise from a dropping funnel over 2 hours, and polymerization was carried out at 80 ° C. with stirring. Further, after adding 18 g of a 1% aqueous solution of ammonium persulfate, the temperature was raised to 85 ° C., and polymerization was carried out for 2 hours to obtain a polymer emulsion.

Comparative Example 7 Emulsion polymerization was carried out according to the method of Example 11 except that the same weight of sodium dodecylbenzenesulfonate was used instead of (Modifier X1) to obtain a polymer emulsion.

Comparative Example 8 Polymerization was carried out according to the method of Example 11 except that the same weight of sodium sulfopropyl methacrylate was used instead of (Modifier X1). No emulsion was obtained.

Evaluation of the polymerization conversion of the monomers of Example 11 and Comparative Example 7, the amount of coagulum formed, the mechanical stability of the emulsion, the chemical stability, the foaming properties, the water resistance and the adhesion of the dried coating film. Table 2 shows the results.

[0056]

[Table 2]

From the results shown in Table 1, the modifier of the present invention is excellent in storage stability, does not inhibit polymerization with a monomer, and has a high conversion. Further, from the results in Table 2, the polymer emulsion obtained by using the modifier of the present invention as an emulsifier for emulsion polymerization has low foaming properties and is excellent in chemical stability and mechanical stability. The film obtained from the polymer emulsion has excellent water resistance and adhesiveness. Furthermore, after removing the resin component from the polymer emulsion, the COD of the wastewater (filtrate) is also low, and the load of the wastewater treatment step is reduced.

[0058]

EFFECTS OF THE INVENTION The modifier of the present invention is excellent in storage stability, increases the monomer polymerization rate as compared with known anionic monomer modifiers, and improves the performance (polymerization degree, antistatic property). The resulting polymer emulsion has excellent mechanical stability and chemical stability, has low foaming properties, and is obtained from a polymer emulsion having improved foaming properties. The coating has excellent water resistance and adhesiveness,
And the like. In addition to the above effects, the modifier of the present invention does not impair the transparency of the polymer film, can impart hydrophilicity to the polymer, dust on the surface of the polymer film, oil, dirt, etc. It has an effect that dirt is hardly adhered, and even if it is adhered, it can be easily removed.
Furthermore, when removing the polymer from the emulsion,
There is also an effect of providing a polymer emulsion in which an emulsifier hardly flows out into wastewater.

────────────────────────────────────────────────── ─── Continuing from the front page Examiner Susumu Sugihara (56) References JP-A-60-170611 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08F 2/00-2 / 60 C08F 246/00-291/18

Claims (11)

(57) [Claims] 1. A sulfate ester represented by the general formula (1) or a salt thereof (A), a phenol polymerization inhibitor (B1) and / or an amine polymerization inhibitor (B2): 50 to 3.0.
00 ppm and copper ion (C) 0.01 to 20 pp
A copolymerizable modifier for polymers consisting of m (Wherein, R is a hydrogen atom or a methyl group, A is an alkylene group, M is a monovalent or divalent cation, and (OA) _n
Represents a polyoxyalkylene group. n is a number from 2 to 30,
m is 1 or 2 and represents the valence of a cation. ) 2. The method according to claim 1, wherein the phenolic polymerization inhibitor (B1) is hydroquinone monomethyl ether.
Copolymerizable modifier. 3. A copolymerizable modifier according to claim 1, wherein the amine-based polymerization inhibitor (B2) is phenothiazine. 4. The method according to claim 1, wherein the polyoxyalkylene chain contains two or more oxypropylene groups.
Copolymerizable modifier. 5. The method according to claim 1, further comprising a buffer (D).
5. The copolymerizable modifier according to any one of items 4 to 4. 6. The copolymerizable modifier according to claim 5, wherein said buffer (D) is citric acid or a salt of citric acid. 7. The anionic monomers in the preparation of the ethylenically unsaturated monomers of the polymer by copolymerizing a method of performing modification copolymerizable modifier according to any one of claims 1 to 6 A method for modifying a polymer using a filler. 8. The method according to claim 1, wherein the ethylenically unsaturated monomer is an unsaturated monomer.
Modification method according to claim 7, wherein for the emulsion polymerization in the presence of a copolymerizable modifier according to any one. 9. The method according to claim 7, wherein the copolymerizable modifier is used in an amount of 0.1 to 20% by weight based on the total weight of the monomers. 10. A polyalkylene glycol (meth) acrylate containing copper ions (C) and a phenol-based polymerization inhibitor (B1) and / or an amine-based polymerization inhibitor (B
A method for producing a copolymerizable modifier for a polymer, characterized in that a sulfation reaction is carried out by adding 2) in advance to produce the modifier according to claim 1. 11. The polymer according to claim 10, wherein at least copper ion (C) and a phenolic polymerization inhibitor (B1) are previously added to the polyalkylene glycol (meth) acrylate, and a sulfation reaction is carried out with sulfamic acid. A method for producing a copolymerizable modifier.