JPS62121717A - Production of comblike amine copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer which can give a thermoplastic molding resin of excellent antistatic properties, by reacting a specified high-MW monomer with an aminoalkyl group-containing vinyl monomer and a copolymerizable vinyl monomer. CONSTITUTION:20-80wt% high-MW (number-average MW of 1,500-20,000) monomer (A) having a polymeric part of a vinyl monomer (e.g., methyl methacrylate) and one polymerizable vinyl group bonded to one of its terminals is reacted with 80-20wt% aminoalkyl group-containing vinyl monomer (B) which comprises a (meth)acrylate (a) having an aminoalkyl group as an ester residue and/or a (meth)acrylamide (b) having an aminoalkyl group as a nitrogen substituent and 0-60wt% monomer (C) copolymerizable with components A and B [e.g., a (meth)acrylate having a polyoxyethylene chain as an ester residue] in a solvent in the presence of a polymerization initiator.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an amine-based comb copolymer, particularly,
This invention relates to a method for producing a comb-shaped copolymer that can be blended with a thermoplastic resin for molding to improve the antistatic effect of the resin.

``Prior art'' Thermoplastic resins for molding, which are used to manufacture housings and parts for electrical products and office equipment, have excellent electrical insulation properties, so they are widely used as molding materials for these housings. ing. However, thermoplastic resins for molding are generally easily charged with electricity, which not only causes dirt and dust to adhere to the surface of the molded product, impairing the appearance of the product, but also allows the molded product to be used in electronic products, office equipment, etc. In the case of a housing, there were problems such as causing malfunction of the contacts of switches and the like.

In order to solve these problems, conventional methods have been used, such as applying an antistatic agent to the surface of a molded article or kneading an antistatic agent into a thermoplastic resin material for molding.

However, in the method of applying an antistatic agent to the surface of the molded product, the antistatic agent becomes less effective due to changes over time or due to washing, etc.
] The disadvantage is that the thin film of the shavings peels off, the antistatic effect is easily lost over time, and the process of applying an antistatic agent is required separately from the molding process, resulting in low productivity of molded products. was there.

Moreover, the method of kneading an antistatic agent into a thermoplastic resin for molding solves problems such as peeling of a thin film of the antistatic agent and a decrease in productivity. However, the antistatic effect decreases due to stains on the surface of the molded product due to bleed-out of the antistatic agent.
Problems such as deterioration of the appearance of the molded product and decrease in antistatic effect due to changes in the antistatic agent mixed in over time were not sufficiently improved.

Generally, conventional antistatic agents are compounds with polar groups, so they have poor compatibility with thermoplastic resins for molding, and if a large amount is kneaded into them, the physical properties of the fat will deteriorate, so it is not necessary. This is because it was not possible to mix in a sufficient amount to obtain a strong antistatic effect and its sustainability.

In addition, thermoplastic resins can be made by copolymerizing vinyl monomers with ionic residues with polymerizable monomers that make up thermoplastic resins and introducing ionic structural units into the copolymer. There are ways to improve the antistatic effect, but
In this method, the ionic structural units were uniformly dispersed in the resin on the order of the molecular size, so the effect on static prevention 1 on the surface of the resin was small. Therefore, in order to obtain a sufficient antistatic effect, it is necessary to introduce a large amount of ionic structural units into this type of thermoplastic resin, which not only causes a decrease in the physical properties of the resulting thermoplastic resin, but also sometimes There was a problem that the resulting resin was of a different nature.

[Problem to be Solved by the Invention 1] The present inventors have arrived at the present invention as a result of intensive studies aimed at obtaining a compound with an excellent long-lasting antistatic effect.

The present inventors obtained a copolymer into which an amine salt structure, which is considered to have the greatest contribution to conductivity, was introduced, and achieved the fifth antistatic effect of thermoplastic resin for molding. It has been found that the product has very good durability.

That is, the above-mentioned object 1] of the present invention is vinyl-based 1it 9
has a polymeric portion of the body and one polymerizable vinyl group bonded to one end thereof, and has a number average molecular weight of 1,
High molecular weight monomers ranging from 500 to 20,000 (1
) 20 to 80% by weight, aminoalkyl-containing vinyl monomer (IT) 80 to 20% by weight, polymeric polymer (IT)
1), and aminofurkyl group-containing vinyl monomer (
Vinyl group electrolyte (■) which can be copolymerized with 1'l) 0 to 60
This is achieved by a method for producing an amine-based comb copolymer, which is characterized by reacting with % Ia.

The high molecular weight monomer N) constituting the comb copolymer obtained by the method of the present invention refers to a high molecular compound having a polymerizable vinyl group bonded to one end of the polymer portion.

Its number average molecular weight is in the range of 1,500 to 20.000,
Preferably it is in the range of 3,000 to 15,000. High molecular weight monomer 1k(T)θ) #*Mt+-7-47
)y++r1-ζnn)nzk3b1> Microphase separation of the obtained comb-shaped copolymer is difficult to occur, and as a result, the compatibility with the thermoplastic resin for molding decreases, which is not preferable. Moreover, when the number average molecular weight exceeds 20,000, when copolymerizing the high molecular weight monomer (1) with other monomers to obtain a comb-shaped copolymer, components that do not have a comb-shaped Vt structure may be used. is undesirable because it increases the production of , making it difficult to obtain the desired comb-shaped copolymer.

In the present invention, the high molecular weight monomer (1) is suitably one in which the polymer portion consists of a vinyl monomer. If the polymer part is made of a monomer other than vinyl monomers, for example, a condensation polymer part such as polyester, polyether, or polyamide, molding thermoplastic This is not preferred because of its low solubility and the lack of a suitable solvent for producing the comb copolymer.

Bi constituting the polymer portion of the high molecular weight monomer (1).

Examples of the monomer include acrylic acid, methacrylic acid, or alkyl esters thereof having 1 to 10 carbon atoms, styrene, α-methylstyrene, 0-1L
Ω-1 or p-vinyltoluene, mixtures thereof,
Examples include nuclear halogenated styrene, a-1 or β-vinylnaphthalene, and the like. Among these, alkyl esters such as acrylic acid or methacrylic acid, particularly methyl methacrylate, are preferred.

The high molecular weight monomer (1) is required to have one polymerizable vinyl group bonded to one end of its polymer portion. If it does not have any polymerizable vinyl groups, it cannot be copolymerized with a vinyl monomer containing an aminoalkyl group, and if it has two or more polymerizable vinyl groups, it cannot be copolymerized with a vinyl monomer containing an aminoalkyl group. This is not preferable because crosslinking occurs when copolymerizing with vinyl monomers containing groups.

The polymerizable vinyl group may be any group as long as it can be copolymerized with other co-In materials constituting the comb copolymer obtained by the method of the present invention. Among these, acrylic groups, methacrylic groups, styryl groups, etc. are preferable because they have excellent copolymerizability.

The polymer portion of the high molecular weight monomer (1) is produced by lanocal polymerization or anionic polymerization.

In the case of lanocal polymerization, persulfates, organic peroxides such as benzoyl peroxide and not-t-butyl peroxide, azo compounds such as azobisisobutyronitrile,
Other commonly used radical initiators are used, or the vinyl monomer is polymerized by thermal polymerization to form the polymer portion of the high molecular weight monomer (T). At that time, a chain transfer agent is used to adjust the number average molecular weight.

At this time, by using a compound having a reactive functional group such as a carboxyl group or a hydroxyl group as a chain transfer agent, a polymerizable vinyl group can be quantitatively introduced at the end of the polymer portion. That is, the chain transfer agent is bonded to one end of the polymer moiety to terminate polymerization, resulting in the formation of a polymer moiety in which the chain transfer agent having a reactive functional group is bonded to the end of the polymer moiety. Ru. By reacting this polymer portion with a compound having a polymerizable vinyl group,
A high molecular weight monomer (1) used in the present invention is obtained.

Examples of the chain transfer agent having a reactive functional group include hydroxyalkyl mercaptans such as hydroxyethyl mercaptan and hydroxypropyl mercaptan, thioglycolic acid, mercaptopropionic acid, and thiosalicylic acid.

Moreover, - as the compound having the above polymerizable vinyl group,
acrylic acid, methacrylic acid, and their acid chlorides,
Examples include glycidyl acrylate and glycidyl methacrylate.

When producing the polymer portion of the high molecular weight monomer (I) by anionic polymerization, an alkyl alkali metal compound such as an alkyl lithium compound represented by 11-butyl lithium and 5ec-butyl lithium is used as a polymerization initiator. . In this case, the number average molecular weight of the polymer portion can be adjusted by adjusting the amount of polymerization initiator used.

When anionic polymerization is used, a so-called living polymer is obtained in which an alkali metal such as lithium is bonded to the end of the polymer portion, and a halogen compound containing a desired polymerizable vinyl group, such as acryl chloride or methacryl chloride, is added to this. , chloromethylstyrene, etc., the high molecular weight monomer (I) used in the present invention can be obtained.

As the monomer that is copolymerized with the high molecular weight monomer (1) to form the comb-shaped copolymer, a vinyl monomer (IT) containing an aminoalkyl group is suitable.

The aminoalkyl group-containing vinyl monomer (II) forms the main chain of the comb copolymer obtained by the method of the present invention, and
The aminoalkyl group is concentrated in the surface layer of the molded product when the comb copolymer is blended with a thermoplastic resin for molding, and has the effect of improving the surface properties of the molded product.
The ammonium salt or quaternary salt improves the antistatic effect and its durability to a great extent.

As the vinyl monomer (II) containing an aminoalkyl group, an ester of acrylic acid or methacrylic acid (A) having an aminoalkyl group as an ester residue, and an acrylamide having an aminofulkyl group as a nitrogen substituent, or Methacrylamide (I3) is mentioned.

In the above structural formulas (A) and (B), R1 is hydrogen or a methyl group, and R2 and R3 are alkyl groups having 1 to 5 carbon atoms, but the smaller the number of carbon atoms, the more effective it is. . n can be selected in the range of 1 to 5, but 2 or 3
are effective.

The ami7 alkyl group of the monomer shown by the above structural formulas (A) and (B) ultimately exerts an antistatic effect as an ammonium salt or a quaternary salt (C).

-(CHz)nN"-R-X-(C)R1 In the above structural formula (C), R and X are HCI.

CH, CI, CH-Br, CHsISC2HsBr-C
6tl, CH2Cl, (CH3), S2O, etc., among which HCI and CH3Cl are particularly effective, and C21'15Br, C6I(, CH2Cl, etc.) are the second most effective.

When an aminoalkyl group is made into an ammonium salt or a quaternary salt, it may be made into a salt at the vinyl monomer stage and then copolymerized with a high molecular weight monomer to produce a comb-shaped copolymer. Alternatively, a method may be employed in which a comb-shaped copolymer is first produced in the form of an aminoalkyl group-containing vinyl monomer, and then the ami-7 alkyl group is converted into a salt. Furthermore, it is also possible to produce a comb-shaped copolymer with the aminoalkyl group intact, blend it with a thermoplastic resin for molding to form a molded product, and then convert the aminoalkyl group into a salt.

The comb copolymer obtained by the method of the present invention has a high molecular weight Jl
By containing a vinyl monomer (III) copolymerizable with the t-mer (+) and the aminoalkyl group-containing vinyl monomer (U), the antistatic effect can be further improved. . The vinyl monomer used here (
m) is not particularly limited as long as it can be copolymerized with the high molecular weight monomer (1) and the aminoalkyl group-containing vinyl monomer (II), and To adjust the amount of ammonium salts (including quaternary salts) or ammonium salts (including quaternary salts), which are frR functional groups, present in the comb copolymer, etc. You can select it as appropriate.

Specific examples of the vinyl monomer (III) include acrylic acid alkyl esters, methacrylic acid alkyl esters represented by methyl methacrylate, substituted styrenes such as α-methylstyrene and p-methylstyrene, acrylonitrile, Examples include nitrile compounds such as methacrylonitrile, 1,2-substituted olefins such as maleic anhydride, maleic ester, maleonitrile, 7-malate ester, and 7-malonitrile, and vinyl ethers. Examples of the vinyl monomer having a hydrophilic group include acrylamide, methacrylamide, nitrogen-substituted compounds thereof, and acrylates and methacrylates having polyoxyethylene as an ester residue.

As the vinyl monomer (T[I), in addition to those exemplified above, ionic compounds can also be used.

For example, by using a vinyl monomer having an anionic functional group, an amphoteric comb copolymer can be obtained. Such amphoteric comb copolymers are characterized by extremely good stability compared to conventional betaine type amphoteric surfactants. As such vinyl monomers,
Examples include acrylic acid and its salts, p-styrenesulfonic acid and its salts, itaconic acid, maleic acid, and hexamaric acid.

The above vinyl monomer (I'll) may be used alone, or 2N! The following may be used in combination.

The content of each monomer contained in the comb copolymer obtained by the method of the present invention is 20 to 80% by weight of high molecular weight monomer (1).
, preferably 40 to 60% by weight, aminoalkyl group-containing vinyl monomer (II) 80 to 20% by weight, preferably 50 to 30% by weight, high molecular weight monomer (N and aminoalkyl group-containing vinyl monomer (II) 'lj !f, vinyl monomer (II) O''-60% by weight, which can be copolymerized with body (IT);
Preferably, it is 10'·-30% heavy electric current.

If the content of the high molecular weight monomer (+) is less than 20 monomers, the compatibility and dispersibility between the comb-shaped copolymer and the molding thermoplastic resin (fat) will decrease, resulting in insufficient antistatic properties. No effect is obtained. In particular, the adhesion of the comb-shaped copolymer concentrated in the surface layer of thermoplastic resin molded products to the tM resin surface is weak and it easily falls off. The same can be said when the content of the !lj dispersion (II) exceeds 80% by weight.When the content of the high molecular weight monomer (1) exceeds 80% by weight, ammonium, which is a !91 functional group, Because the amount of salt (quaternary salt) is small, a sufficient antistatic effect cannot be obtained.The same thing happens when the content of the aminoalkyl group-containing vinyl monomer (II) is less than 20% by weight. The same can be said.

A vinyl monomer (I) copolymerizable with the high molecular weight monomer (1) and the aminoalkyl group-containing vinyl monomer (II).
ll) is used for the purpose of adjusting the amount of functional groups or introducing a third functional component (imparting hydrophilicity, etc.), so it should not be used especially when it is not necessary. You don't have to. Moreover, if the content exceeds 60% by weight, the sustainability of the antistatic effect will decrease, which is not preferable.

The polymerization method for producing the comb copolymer according to the method of the present invention may be any method such as mixed liquid polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization. Among these methods, solution polymerization is the most suitable. In this case, the solvent must be selected depending on the solubility of the component monomers. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, diethyl ketone, and butyl methyl ketone, benzene, toluene, xylene, tetrahydro7rane, methanol, and ethanol.

These solvents may be used alone or in combination of two or more, but since the comb-shaped copolymer is composed of parts with different properties, it is difficult to use the mixing groove or during polymerization.
It is preferable to use commonly used polymerization initiators. Polymerization initiators that can be used include azo compounds such as azobisisobutyronitrile, and Lanocal initiators typified by peroxides such as benzoyl peroxide;
When using a polar solvent, potassium persulfate and the like can be mentioned.

The comb-shaped copolymer obtained by the method of the present invention is used by blending it with a thermoplastic resin for molding. The content is 1 to 10% by weight, calculated as the amount of aminoalkyl group (ultimately ammonia cum salt or quaternary salt).
．． It is preferable to mix 5 to 13% Iλ%.

The thermoplastic resins for molding that can be blended with the comb copolymer obtained by the method of the present invention include polystyrene, rubber-reinforced polystyrene, styrene-acryloni) + full copolymer, ABS resin, MBS resin, A, ESI[ t, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, polyacrylic ester, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyacetal, polypropylene, polyethylene, doryamides, silicone resin, polyethylene terephthalate, polybutylene terephthalate , polyphenylene oxide, polycarbonate, etc., but are not limited to these examples.

[Effects of the Invention 1] The present invention has the following particularly remarkable effects, and its industrial utility value is extremely large.

(1) The comb copolymer obtained by the method of the present invention is
Its surface resistance is as low as 10'Ω, making it an exceptionally good ionic conductive material.

(2) The comb copolymer obtained by the method of the present invention is
Blended with thermoplastic resin for molding, molded and used,
The surface resistance of the obtained molded product is IQIO.

The level can be as low as Ω.

(3) In the comb copolymer obtained by the method of the present invention, the anchor portion improves compatibility and dispersibility with the thermoplastic resin for molding, so the portion blended into the molded product will not bleed.
There is no out-of-striping process, and the excellent antistatic effect can be maintained throughout the application period.

[Example 1] The present invention will be specifically explained below based on Examples and Comparative Examples, but the present invention does not exceed the gist thereof.
It is not limited to the following examples.

In each of the following Examples and Comparative Examples, the antistatic effect was evaluated by measuring the surface resistance and charging half-life of the molded article.

The surface resistance is I-reu+Iett-Packa
Re5istivity Ce1l/Hi manufactured by rd company
Measured using gb Re5stance Meter. The test piece is 8 can x 8 eta x
1+n+a was used.

The charging half-life is 5bisl+ido & Co.
taticHonestometer Type
S-4104''.The measurement conditions were an applied voltage of 8000 V, a temperature of 23° C., and a humidity of 50%.

Note that the antistatic effect is determined to be better as the measured values of surface resistance and charging half-life are smaller.

Example 1 i) Production of polymer @jlLmer Methyl ethyl ketone (hereinafter referred to as MEK) 50085
Methyl methacrylate (hereinafter referred to as MMA) 1, . 5
00. , and 40 g of thioglycolic acid were placed in a 31 flask equipped with a stirrer, and the temperature was raised to 50°C under a nitrogen stream. Next, 10 g of azobisisobutyronitrile (hereinafter referred to as AIBN) was added as a polymerization initiator to start the polymerization reaction.

Seven and a half hours after the start of the polymerization reaction, hydroquinone was added to the m-combined yarn to stop the polymerization reaction.

The reaction solution was diluted by further adding MEK500FK, and then poured into a large excess of hexane to obtain a polymer of MMA with thioglycolic acid bonded to the terminals. This polymer was purified by reprecipitation twice using MEK/hexane system, and then dried. The yield was 4208. Moreover, the number average LAt of the obtained polymer is −4 ml+Q 9 11
xylene 200. .

” 200 g of bipolymer, glycidyl methacrylate 6.
28 and p-methoxy7ethyl(2+n)H were charged, and the above polymer was dissolved while raising the temperature. When the internal temperature of the flask reached 100°C, 0.95 g of N,N-trimethyllaurylamine was added, and the temperature was further raised to 130°C and the reaction was carried out for 5 hours.

After the reaction was completed, a portion of the reaction solution was collected and acid-base titration was performed to confirm that the -COOH group of thioglycolic acid bonded to the terminal of the bipolymer had disappeared. Then MEK
The mixture was diluted 3 times with the addition of MMAi, and then poured into a large excess of hexane to make the entire MMAi polymer. The obtained high molecular weight monolayer was further purified by reprecipitation twice using the MEK/hexane system.

Yield was 200g.

(ii) <Production of L-type copolymer 70 g of MMA-based high molecular weight monomer obtained in (i), 70 g of dimethylaminoethyl methacrylate (hereinafter referred to as DMA)
g, and (/'MEK1408 with a stirring device)
After charging into a 0+n17 lasco, heat to 70°C while stirring.
The temperature was raised to 100% to dissolve the mixture. Next, 1 sg of AIB No. was added to start the polymerization reaction.

After 6 hours had passed from the start, the reaction solution was poured into a large excess of hexane to precipitate a DMA/MMA<L-type copolymer. The obtained comb-shaped copolymer was further purified by reprecipitation twice using an MCK/hexane system, and then dried. Yield is 1
It was 20g.

The conversion rate was 85.9%. Also, the results of elemental analysis DM
A/MMA< DMA+ in the L-type copolymer is 39.
It was 9% by weight. The coulometric average molecular weight measured by gel vermicin chromatography 7 (GPC) method was about 100,000, and it was found that there was very little residual MMA-based high molecular weight material.

(iii) DMA / MMA < L
DMA/MMA<
l, press-molded the mold copolymer at 190°C to 8 cm.
A sheet of X 8 cm X I Ifim was prepared. On the other hand, this comb-shaped copolymer is a polymethyl methacrylate resin (hereinafter referred to as MMA@4 resin).The melt 70-index measured at 220°C and 10 kg is 3.9 g/++'1 min. ) and blend (18
Roll at 0°C.

Magnenium stearate 0.3% as a lubricant
(Required) After shirring, press molding was carried out under the conditions of γ length 19 f)'C to prepare a similar sheet. The remaining DMA component in the composition was 3% by weight. These two types of sheets were brought into contact with hydrogen chloride gas for 24 hours to convert the DMA component into ammonium salt. Thereafter, these sheets were thoroughly washed with water and then stored at constant temperature and humidity (23° C., 50% RH).

(iv) Conductivity of DMA/MMA<I, type copolymer, and blend composition Note: The surface resistance of the two types of sheets is 2×10 after 1 day of storage for the molded product made of the comb type copolymer itself.
'Ω/cm, 1.5X10'Ω/ CII after 14 days of storage
I, for molded products made of a blend composition of comb copolymer and MMA resin, G, 6X10'Ω after 1 day of storage
/cII11 after 14 days of storage 1.2X10'Ω/cL11
As a result of measuring the charging half-life, no charging of the molded product was observed.

Example 2 I) Production of high molecular weight monomer In the same manner as in Example 1, the polymerization temperature was set at 60°C.
A polymer having -COOH groups at the terminals was obtained. The number average molecular weight of this polymer was 6,800. Using this polymer, an MMA-based high molecular weight monomer was obtained in the same manner as in Example 1.

(Ii) Production of comb-shaped copolymer MMA-based polymer electromonomer 608 obtained in (i), MM
A90. , 150 g of N,N-dimethylaminopropylacrylamide (hereinafter referred to as DMP 8), and MEK3
00g was charged into a No. 11 flask, and the temperature was raised to 70°C to dissolve it. Next, 12 g of AIBNO was added to start the polymerization reaction. After 7 hours from the start, same as in Example 1.

A DMPA/MMA<L-type copolymer was obtained by the method, and purified and dried. The conversion rate was 71.0%, D in the comb copolymer
The MPA component was 33.0% by weight.

1:::1 nuDA/MuA/17E north fFz4
Preparation of the f-prene V composition and blending the DMPA/MMA < diamond copolymer obtained from the ammonium chloride reaction (ii) into MMA $4+ fat with the MMA resin in the same manner as in Example 1 After rubbing, the temperature is 190℃
Press molding under the conditions of 8 c+oX 8 C+6X
1 +o+a sheet was created. The amount of DMPA component in the blend composition was 3.0% by weight. This sheet was brought into contact with hydrogen chloride gas for 24 hours to convert the DMPA component into ammonium salt. Thereafter, this sheet was thoroughly washed with water and then stored at constant temperature and humidity (23° C., 50% RH).

(iv) The surface resistance value of the conductive sheet of the DMPA/MMA<L-type copolymer blend composition is 1.3X1 after 1 day of storage.
010Ω/c111, 3.2×101°Ω after storage 140
/Qllll. The charging half-life was 1 second or less after 1 day of storage.

Example 3 (i) Preparation of high molecular weight monomer In the same manner as in Example 2, the number average molecular weight monomer 6,8
A 00 MMA-based polymer ff1111 body was obtained.

(ii) <Production of L-type copolymer In the same manner as in Example 2, DMPA/MMA<
An L-type copolymer was obtained.

(iii) Quaternization reaction of DMPA/MMA< L-type copolymer with benol chloride and production of blend composition 50 g of DMPA/MMA< L-type copolymer obtained in (ii) Hydro 7 run (hereinafter referred to as THF)
/ methanol mixed solvent. Next, 1.2 parts of benzyl chloride (hereinafter referred to as 82C1) was added per 7 groups of DMPA, and the mixture was reacted at 50°C for 24 hours.

After the reaction was completed, the solvent and excess BzCl were removed under reduced pressure. The obtained reaction product was approximately GO), and it is presumed that the quaternization reaction occurred quantitatively.

The thus obtained DMPA/MMA<L-type copolymer BzCI salt was blended with MMA resin in the same manner as in Example 1, and then press-molded at a temperature of 190°C to form a 8c A sheet of 8 cm x 1 tnn+ was prepared. The amount of DMPA-containing component in the blend composition was 3.0% by weight. This sheet is heated at constant temperature and humidity (2
It was stored at 3°C, 50% RH).

(iv) DMPA/MMA< L-type copolymer BzC
The surface resistance value of the conductive sheet of the salt blend composition was 3.7×1 after 1 day of storage.
010Ω/em, after 7 days of storage 1,7X1010Ω/
cIll, after 14 days of storage2. It was 1×109Ω/cm. The charging half-life was 1.5 seconds after one day of storage.

Example 4 (i) Preparation of 91 high molecular weight monomers In the same manner as in Example 2, the number average molecular weight was 6.8.
00 MMA-based high molecular weight monomer was obtained.

(ii) <Production of L-type copolymer In the same manner as in Example 2, DMPA/MMA<
An L-type copolymer was obtained.

(iii) DMPA/MMA<1. 50 g of the DMPA/MMA<L type copolymer obtained in the quaternization reaction of the type copolymer with ethyl bromide and the production of the blend composition (11) was dissolved in a THF/metal/metal mixed solvent. Ta. Next, ethyl bromide (hereinafter referred to as EtBr) was added in an amount of 1.5 equivalents based on the 7 groups of DMPA, and the mixture was reacted at 40°C for 48 hours. After the reaction was completed, the solvent and excess EtBr were removed under reduced pressure. The reaction product obtained was about 61 tr, and it is estimated that the quaternization reaction occurred almost quantitatively.

The thus obtained DMPA/MMA < L type copolymer ELBr salt was blended with MMA resin in the same manner as in Example 1, and then press-molded at a temperature of 190°C to form a 8 cm× A sheet of 8 cm×1+n+n was created. The DMPΔ conversion component 1 in the blend composition was 3% by weight. This sheet is kept at a constant temperature (23
℃, 50% RH).

(iv) DMP A / MMA <
Surface resistance for conductive sheet of L-type copolymer EtBr salt blend composition 7&l+I"1-ff 1 Extra-oral A Q Vln II ^/-, -IQ left after 7 days 2
．． 4×10”Ω/am, 1.7× after 14 saves 14 ma
1010Ω/cII. The half-life of charging is approximately 5 days after storage.
It was seconds.

Example 5 (i) Production of high molecular weight monomer In the same manner as in Example 2, a number average molecular weight of 6,8
00 MMA-based high molecular weight monomer was obtained.

(ii) <Production of L-type copolymer quaternary salt 30 g of MMA-based high molecular weight monomer obtained in (i), MM
A30g, CH3 of trimethylamino/ethyl acrylate
40 g of Cl quaternary salt (hereinafter referred to as TMA).

and dimethylformamide (hereinafter referred to as DMF) 1
00g was charged into a 3001617 flask and the temperature was raised to 70"C to dissolve it. Next, ATBNO0II? was added to start the polymerization reaction. After 5.2 hours had passed from the start of the reaction, the polymerization reaction was stopped. After stopping, the reaction solution was poured into a large excess of acetone/hexane mixed solvent to precipitate the reaction product.Next, it was dissolved and dispersed in MEK/ethanol/ethanol solvent, and reprecipitated in hexane. Viscous 6-obtained TM
The amount of TMA component in the A/MMA comb copolymer was 46.
It was 9% by weight.

(iii) TMA/MMA < TMA/MMA obtained in ii) < L-type copolymer N for production of L-type copolymer blend composition
MMA tJ in a similar manner as in Example 1.
(styrene-acrylonitrile resin (hereinafter referred to as S)
After blending with resin A), the mixture was press-molded at a temperature of 190°C to create a sheet of 8 cm x 8 co+X11. The amount of TMA component in the blend composition is
The amount of nitrogen derived from TMA was made to be the same as the amount of nitrogen in the compositions in Examples 1-4 above. These sheets were stored at constant temperature and humidity (23"C150%RH).

(iv) TMA/MMA< The surface resistance value of the conductive sheet of the L-type copolymer blend composition is 8.0×1 after 1 day of storage in the case of the composition blended with MMA rJf fat.
08Ω/cm, after 7 days of storage 6.6X10”Ω/clll
.

After 14 days of storage, it was 7.7×10′Ω/cm. In the case of a composition blended with SA resin, 2.0X after 3 days of storage
It was 109Ω/cIfl. No charging was observed in any of the resin compositions.

Comparative Example 1 (i) Production of high molecular weight monomer In the same manner as in Example 1, the number average molecular weight was 9.2.
00 MMA-based high molecular weight single enemy was obtained.

(ii) <Production of C-type copolymer 40 g of the MMA-based high molecular weight monomer obtained in (i).

MMA 3 og, acrylic acid (hereinafter referred to as AA) 30
g.

and MEKloog were placed in a 300+a17 flask and heated to 70°C to dissolve. Next, AIBNo, 1g
was added to start the polymerization reaction. 5 after starting the reaction
After a lapse of time, hydroquinone was added to stop the polymerization reaction, and the reaction solution was poured into a large excess of ethyl ether to precipitate the reaction product. This reaction product was purified by reprecipitation using MEK/hexane. The yield was 77.2g.

The AA acid component in the obtained AA/MMA<L-type copolymer was 18.8% by weight.

(iii) T The Na salt of the AA/MMA comb copolymer was prepared by dissolving the copolymer in HF/methanol), then adding a NaOH/methanol solution containing an Na component equivalent to the AA component and leaving it for 3 hours. . Furthermore, in a similar way,
A Li salt of AA/MMA<L type copolymer was produced using LiOH.

These Na salts and Li salts were blended into MMA resin and SA resin, respectively, in the same manner as in Example 1, and then press-molded at a temperature of 190°C.
A sheet of c+aX 8 c+aX 1 +a+a was created. AA-Na and AA-Li in the blend composition
The component amounts were such that the AA-Na group and the AA-Li group had the same number of moles per unit weight of the composition as the amide group (or ammonium group) in Examples 1 to 4. At this time, the Na salt had poor compatibility with the MMA resin and could not be uniformly dispersed when blended.These sheets were kept at constant temperature and humidity (23℃, 50% R
Stored under H) condition.

(iv) AA/MMA < L, the surface resistance value for the conductive sheet of the type copolymer Na salt and Li salt blend composition is, in the case of Na salt, MMA
The composition blended with Jugo is 1.6 x 10" after 3 days of storage.
Ω/cI6. In the case of Li salt, the composition blended with MMA resin is 9.0×10”070ml after 1 day of storage.
After 7 days of storage, it is 8.0 x 101 Ω/c+++, after 14 days of storage, it is 2.4 x 10'2 Ω/e IQ, and for the composition blended with SA resin, it is 6.6 x 10 10 Ω after 3 days of storage.
/c+o.

In the case of a composition containing a blend of Li salt and SA resin, the charging half-life was 11 seconds after one day of storage.

It is clear that comb copolymers containing Na salts and Li salts have poor compatibility with thermoplastic resins for molding, and that the antistatic effect of the resulting molded products is inferior to that of comb copolymers containing amine salts. It is.

Comparative Example 2 (i) Production of high molecular weight monomer By the same method as in Example 1, the number average molecular weight was 9.
, 200 MMA-based high molecular weight monomer was obtained.

(ii) <Production of L-type copolymer 40 g of MMA-based high molecular weight monomer obtained in (i), 1)
- Sodium styrene sulfonate (hereinafter referred to as PSS) 30
I? , 30 g of MMA, and 35 og of DMF were placed in flask No. 11, and the temperature was raised to 70° C. to dissolve them.

Next, 1 g of AIBNo was added to start the polymerization reaction.

At this time, as the polymerization reaction progressed, the reaction solution gradually became non-uniform. 17 hours after the start,
The polymerization reaction was stopped, and the reaction solution was poured into a large excess of acetone to precipitate the reaction product. Obtained PSS/MM
The A<L type copolymer had a conversion rate of 57.5%, and the amount of PSS component in the copolymer was 30.1% by weight.

(iii) Production of PSS/MMA<L-type copolymer blend composition (i;) PSS/MMA<L-type copolymer obtained in step (i;),
After blending with MMA resin in the same manner as in Example 1, it was press-molded at a temperature of 190"C to give 8c.
A sheet of τo×8c x 11n was prepared. The amount of PSSSS component in the blend composition is as follows: Example 1 and 4
The number of moles per unit weight of the composition was made to be the same as that of the amine 7 group in the composition. During blending, some poor dispersion was observed. This sheet was heated at constant temperature: fA (23'C, 50%
RH).

(iv) PSS/MMA< The surface resistance value of the conductive sheet of the L-type copolymer composition is 1.8×1 after 1 day of storage.
011Ω/cI+1, 5.4X10'2Ω/ after 7 days of storage
The era was 4.4×10 Ω/eIa after 14 days of storage. The charging half-life was 15 seconds after one day of storage.

That is, the antistatic effect, its sustainability, and its compatibility with the thermoplastic resin for molding are all inferior to the comb-shaped copolymer according to the present invention.

Comparative Example 3 (i) Production of DMA/MMA random copolymer DMA70g, MMA70g1 and ME
Put K140g into 500+A17 Lasco, AIB
No, 15I? was added, and a polymerization reaction was carried out at 70°C for 6.8 hours. After the reaction is complete, the reaction solution is poured into a large excess of diethyl ether to precipitate the reaction product, and then MEK/
It was purified by reprecipitation with hexane. The obtained [)MA/MM parundum copolymer had a conversion rate of 45.4%, and the DMA component in the copolymer was 50.3% by weight.

(iii) Production of DMA/MMA random copolymer blend composition The DMA/MMA random copolymer obtained in (11) was treated with MMA a (fatty) in the same manner as in Example 1. After blending, a sheet of 8cI6 x 8clII x l111 was prepared by press molding at a temperature of 190°C.The amount of DMAr & in the blend composition was as follows: The amount of nitrogen in Composition 5 was made to be the same as in Composition 5 in ~4.Next.

After contacting this sheet with hydrogen chloride gas for 24 hours,
It was thoroughly washed with water and stored at constant temperature and humidity (23° C., 50% RH).

(iv) DMA/MM parundum copolymer, II'1. The surface resistance value of the sold conductive sheet is 5×1011 after 1 day of storage.
Ω/cm, and 2.6×10”Ω/drfl after 14 days of storage.

The antistatic effect is inferior to that of the comb copolymer of the present invention.

Table 1 shows the measurement results of surface resistance and charging half-life of the above Examples and Comparative Examples.

Claims (6)

[Claims] (1) When producing an amine-based comb copolymer, it has a polymer portion of vinyl monomer and one polymerizable vinyl group bonded to one end thereof, and has a number average molecular weight. High molecular weight monomer (I) in the range of 1,500 to 20,000 20
~80% by weight, aminoalkyl group-containing vinyl monomer (II) 80-20% by weight, high molecular weight monomer (I)
and production of an amine-based comb copolymer, characterized in that the aminoalkyl group-containing vinyl monomer (II) is reacted with 0 to 60% by weight of a copolymerizable vinyl monomer (III). Method. (2) As the aminoalkyl-containing vinyl monomer (II), an ester of acrylic acid or methacrylic acid having an aminoalkyl group as an ester residue and/or an acrylamide or methacrylamide having an aminoalkyl group as a nitrogen substituent is used. A method for producing an amine-based comb copolymer according to claim (1). (3) Claim No. 1, characterized in that the aminoalkyl group is an ammonium salt or a quaternary salt (
A method for producing an amine-based comb copolymer according to items 1) and 2). (4) Claims (1) to (3), characterized in that the vinyl monomer constituting the polymer portion of the high molecular weight monomer (I) is methyl methacrylate. A method for producing an amine-based comb copolymer. (5) Claims (1) to (4), characterized in that the vinyl monomer (III) is an acrylate or methacrylate having a polyoxyethylene chain as an ester residue. A method for producing the amine-based comb copolymer described above. (6) Amine-based comb-shaped monomers according to claims (1) to (4), characterized in that the vinyl monomer (III) is one having an anionic group. Method for producing polymers.