JP2528784B2 - Oxyalkylene ether, antistatic agent and resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel oxyalkylene ether, an antistatic agent and an antistatic resin composition. More specifically, ABS, polyester, polystyrene, polyarylate, polyphenylene oxide, polyurethane, polyarylate, polyphenylene oxide,
The present invention relates to an oxyalkylene ether that imparts antistatic property and hydrophilicity by being kneaded into fibers such as polysulfone and polyether sulfone and molding resins.

[0002]

2. Description of the Related Art Heretofore, a resinous adduct of an aromatic divinyl compound and a phenol having an alkyl group having 1 or 2 carbon atoms at the para position as a substituent has been known. The manufacturing method is disclosed in U.S. Pat.
No. 6510. Polyethylene glycol (average molecular weight of 1,000 to 20,000), higher alcohol ethylene oxide adducts, phenolic ethylene oxide adducts, etc. are used as antistatic agents such as fibers and molding resins and hydrophilicity-imparting agents. Has been.

[0003]

However, the above-mentioned antistatic agents and hydrophilicity-imparting agents, when kneaded into fibers or molding resins, have insufficient compatibility or durability with fibers or resins, resulting in fibers or resins. It is difficult to knead uniformly, and there is a problem in that the effect does not continue due to slipping out or bleeding out due to dry cleaning or washing with water.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies as to the derivative of the above resinous adduct, and as a result, found a new oxyalkylene ether, and the oxyalkylene ether has a compatibility with fibers and resins. It was found that the antistatic property and the hydrophilic effect are kept high even after dry cleaning or washing with water, and the present invention has been accomplished.

That is, the present invention is an oxyalkylene ether of a phenol / divinylbenzene addition polymer represented by the following general formula (1). (In the above formula, Ar is a residue of phenol, Ph is m- and / or p-phenylene group, Q is an alkylene group having 2 to 4 carbon atoms, m is an integer of 1 to 40, and n is 0 to 15 integer,
The m + 2 n's may be the same or different, and the sum of the m + 2 n's is 1 to 500. ); And an antistatic agent for resins comprising the oxyalkylene ether.

Ar is a residue of phenols (group excluding one hydroxyl group and one or two hydrogen atoms), and the phenols have one substituent at any of the o, m and p positions. The substituent is selected from an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, and an aryl-substituted alkyl group having 1 to 3 carbon atoms. Examples of monocyclic phenols include cresol, xylenol, ethylphenol, propylphenol, nonylphenol, hydroquinone, resorcin, catechol and guaiacol. Examples of polycyclic phenols include phenylphenol, cumylphenol, benzylphenol, hydroquinone monophenyl ether, naphthol, benzylnaphthol, and bisphenol A. Preferred are monocyclic phenols, and particularly preferred are m-cresol and p-cresol.

Ph is a phenylene group, and examples of divinylbenzene include o-divinylbenzene, m-divinylbenzene and p-divinylbenzene, with m-divinylbenzene and p-divinylbenzene being preferred. Although divinylbenzene contains ethylvinylbenzene as a main impurity, the content of ethylvinylbenzene is 40% by weight or less, preferably 20% by weight or less.

The phenol / divinylbenzene addition polymer (A) can be obtained by the method described in JP-B-47-6510. That is, it is usually obtained by reacting phenols and divinylbenzene in the presence of a solvent in the presence of a Lewis acid catalyst such as boron trifluoride. Addition of divinylbenzene to phenols is
This is the ortho position. The average molecular weight of the obtained polymer is usually 1,000 to 10,000, preferably 2,000.
~ 7,000.

The catalyst is usually 0.0 with respect to phenols.
Use 5-5% by weight. If it is less than 0.05% by weight, the reaction rate will decrease, and if it exceeds 5% by weight, no improvement in the reaction rate will be observed, which is uneconomical.

The reaction temperature is usually 25 to 150 ° C. Two
If the temperature is lower than 5 ° C, a side reaction such as an addition reaction between divinylbenzenes or an alkylation reaction to divinylbenzene occurs, and if the temperature exceeds 150 ° C, an alkylation reaction to divinylbenzene or a solvent occurs. In any case, the desired alkylated addition polymer cannot be obtained.

As the solvent, aromatic solvents such as benzene, toluene, xylene and methylnaphthalene, hydrocarbon solvents such as hexane and cyclohexane, acetone,
Ketone-based solvent such as methyl ethyl ketone, methanol,
Examples thereof include alcohol solvents such as ethanol, propanol, butanol and octanol, and hydrophilic solvents such as ethylene glycol, polyethylene glycol, polypropylene glycol, ethylene glycol monoethyl ether, dimethylformamide, dimethyl sulfoxide and dimethylacetamide. Aromatic solvents are preferable, and benzene, toluene, and xylene are particularly preferable.

The reaction molar ratio of phenols to divinylbenzene is usually 1: 0.8 to 0.99, preferably 1: 0.8.
It is 0.85-0.96. Divinylbenzene is 0.8
If it is less than the above range, the molecular weight is too low to obtain a resinous material. 0.
If it exceeds 99, the molecular weight becomes too large and handling becomes difficult.

The amount of solvent is usually 20 with respect to phenols.
% To 300% by weight. When the amount of the solvent is less than 20% by weight, the viscosity of the system increases and it is difficult to handle. If it exceeds 300% by weight, the reaction rate is lowered, the reaction takes a long time, and an alkylation reaction to a solvent occurs.

The phenol / divinylbenzene addition polymer (A) is preferably linear.

Oxyalkylene ether (B) of the present invention
Can be obtained by adding an alkylene oxide to the above-mentioned phenol / divinylbenzene addition polymer (A). Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide, and among these, preferred is ethylene oxide or a combination of ethylene oxide and propylene oxide (block or random addition). The addition mole number of alkylene oxide is usually 1 to
It is 500, preferably 20 to 300.

The alkylene oxide may be added by a usual method. That is, a phenol / divinylbenzene addition polymer (A) is dissolved in a solvent, and a catalyst (alkali catalyst such as potassium hydroxide, sodium hydroxide, calcium hydroxide, lithium hydroxide or sodium methylate,
Add a Lewis acid catalyst such as boron trifluoride, etc.) 10
The oxyalkylene ether (B) of the present invention can be obtained by adding alkylene oxide at 0 to 200 ° C. and reacting under pressure.

As the solvent, aromatic solvents such as benzene, toluene, xylene and methylnaphthalene, hydrocarbon solvents such as hexane and cyclohexane, acetone,
Examples include ketone-based solvents such as methyl ethyl ketone and hydrophilic solvents such as dimethylformamide, dimethylsulfoxide, and dimethylacetamide. Aromatic solvents are preferable, and benzene, toluene, and xylene are particularly preferable. The amount of solvent is usually 10 to 300% by weight based on the addition polymer of phenols and divinylbenzene.
Is.

Oxyalkylene ether (B) of the present invention
The oxyalkylene content therein is usually 10 to 95% by weight, preferably 20 to 90% by weight, more preferably 3
It is 0 to 80% by weight. If the oxyalkylene content is less than 10% by weight, the antistatic property and hydrophilicity are insufficient, and if it exceeds 95% by weight, the durability becomes poor.

Oxyalkylene ether (B) of the present invention
Is used as a molding resin such as ABS, polyester, polystyrene, polycarbonate, polyurethane, polyarylate, polyphenylene oxide, polysulfone, and polyethersulfone, and a kneading type antistatic agent for fibers and a hydrophilicity-imparting agent. The resin composition itself can be used, or it can be used in a system dissolved in a solvent. The addition amount of the oxyalkylene ether (B) of the present invention is usually 0.5 to 20% by weight, preferably 3 to 20% by weight based on the molding resin or the fiber.
15% by weight. If it is less than 0.5% by weight, the effect is not sufficiently exhibited, and if it exceeds 20% by weight, the physical properties (strength etc.) of the resin or fiber are deteriorated.

[0020]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Parts in the examples are parts by weight, and% is% by weight.

Example 1 220 g of p-cresol and 260 g of divinylbenzene (Shin Nippon Steel Chemical: DVB-960, m-, p-divinylbenzene content 96%) were reacted by the method described in JP-B-47-6510. Then, a phenol / divinylbenzene addition polymer (A) was obtained. The average molecular weight of the obtained (A) was 4,500 (from GPC), ¹ HNMR, ¹³
It was confirmed to be linear by CNMR. 800 g {(A) obtained by diluting (A) obtained above with xylene.
Content of 300g} 3L autoclave (made by SUS)
, 1 g of potassium hydroxide was added, and after nitrogen substitution, 1
400 g of ethylene oxide was added at 60 ° C. for 8 hours, aged for 5 hours, 3 g of an adsorbent (Kyowa Chemical Industry Co., Ltd .: Kyoward 600) was added, and the mixture was filtered with a spakler filter to obtain the oxyalkylene ether (B) of the present invention Xylene solution (1) was obtained. The content of (B) was 58%, and it was a pale yellow liquid having a viscosity of 56,000 cps (25 ° C.).

Example 2 220 g of m-cresol, divinylbenzene (manufactured by Nippon Steel Chemicals: DVB-810, m-, p-divinylbenzene content 81%, ethylvinylbenzene, were prepared according to the method described in JP-B-47-6510. 18%) 300g of phenol and divinylbenzene addition polymer (A)
I got The average molecular weight of the obtained (A) was 3,500 (G
(From PC), it was confirmed to be linear by ¹ HNMR and ¹³ CNMR. 800 g {(A) content 300 g} obtained by diluting (A) obtained above with xylene is 3
Charged to L autoclave (made by SUS), charged with 1 g of potassium hydroxide, after nitrogen substitution, charged with 300 g of ethylene oxide at 160 ° C. for 8 hours and aged for 5 hours, adsorbent (Kyowa Chemical 600: Kyoward 600) Add 3g,
Filtration with a spakler filter gave a xylene solution (2) of (B) of the present invention. The content of (B) is 55%,
It was a pale yellow liquid having a viscosity of 33,000 cps (25 ° C.).

Example 3 220 g of p-cresol and 260 g of divinylbenzene (manufactured by Nippon Steel Chemical Co., Ltd .: DVB-960, m-, p-divinylbenzene content 96%) were reacted by the method described in JP-B-47-6510. Then, a phenol / divinylbenzene addition polymer (A) was obtained. The average molecular weight of the obtained (A) was 4,500 (from GPC), ¹ HNMR, ¹³
It was confirmed to be linear by CNMR. 800 g {(A) obtained by diluting (A) obtained above with xylene.
Content of 300g} 3L autoclave (made by SUS)
Was charged, 1 g of potassium hydroxide was added, 300 g of ethylene oxide and 50 g of propylene oxide mixed in advance after nitrogen substitution were added in 15 hours, and aged for 10 hours,
3 g of an adsorbent (Kyowa Chemical Co., Ltd .: Kyoward 600) was added, and the mixture was filtered with a spakler filter to obtain (B)
A xylene solution (3) was obtained. The content of (B) is 57%
It was a pale yellow liquid having a viscosity of 35,000 cps (25 ° C.).

EXAMPLE 4 220 g of nonylphenol and 117 g of divinylbenzene (produced by Nippon Steel Chemical Co., Ltd .: DVB-960, m-, p-divinylbenzene content 96%) were reacted by the method described in JP-B-47-6510. A divinylbenzene addition polymer (A) was obtained. The average molecular weight of the obtained (A) was 3,800 (from GPC), ¹ HNMR,
It was confirmed to be linear by ¹³ C NMR. 800 g of the above-obtained (A) diluted with toluene
{(A) content 300g} to 3L autoclave (S
(Made by US), charged with 1 g of sodium hydroxide, purged with nitrogen, charged with 300 g of ethylene oxide at 160 ° C. for 8 hours, aged for 5 hours, and then adsorbed (manufactured by Kyowa Chemical Industry:
3 g of Kyoward 600) was added, and the mixture was filtered through a spacler filter to obtain a toluene solution (4) of (B) of the present invention. The content of (B) is 55% and the viscosity is 28,000c.
It was a pale yellow liquid at ps (25 ° C.).

Performance test Oxyalkylene ether solution (1) of Examples 1 to 4
Using (4) and the following comparative product, compatibility with a resin and antistatic property (after dry cleaning and water washing) were evaluated. The results are shown in Tables 1-5. Comparative product (A) having an average molecular weight of 4,500 obtained in Example (5) Polyethylene glycol having an average molecular weight of 2,000 (6) Polyethylene glycol having an average molecular weight of 10,000 (7) Oleyl alcohol ethylene oxide 30 mol adduct (8) Nonylphenol ethylene oxide 40 mol adduct (9) Test method (1) to (4) of the present invention (without solvent), a comparative product of 8% by weight were added to a molding resin shown below, and a laboratory test was conducted. A plastomill (capacity: 60 ml, manufactured by Toyo Seiki Co., Ltd.) was charged and melt-kneaded at 200 to 300 ° C. and 60 rpm for 5 minutes to prepare antistatic property evaluation resin compositions [1] to [9]. (Blank is not added) Then, using a pressure molding machine, 180-250 ° C, 100K
Hot pressing was performed under a pressure of g / cm ² for 1 minute, and then a 2 mm-thickness square test piece was prepared by cooling with a cooling press at 40 ° C. and 100 Kg / cm ² , and the treatment and conditions described below were used. Surface resistivity was measured. (1) After molding, the square test piece is kept at 20 ° C and humidity is 65%
Leave for 24 hours in RH atmosphere. (2) After molding, the square test piece was washed with Perkren, dried and then left in an atmosphere of 20 ° C. and a humidity of 65% RH for 24 hours. (3) After molding, the square test piece was washed with an aqueous solution of a detergent (Mama Lemon: manufactured by Lion Co., Ltd.), then thoroughly washed with ion-exchanged water, and then the surface water was dried to 20 ° C. and a humidity of 6
Leave in a 5% RH atmosphere for 24 hours. Compatibility was judged by the turbidity of the appearance. ○: No turbidity ×: Partially turbid (molding resin used) ABS resin: JSR-ABS10 manufactured by Nippon Synthetic Rubber Co., Ltd. Polyester resin: (ii) Byroppet EMC-307 manufactured by Toyobo Co., Ltd. (b) Toray Industries, Inc. 1401-X06 (polybutylene terephthalate) Polystyrene resin: Asahi Kasei Co., Ltd. Stylon 600 Polycarbonate resin: Mitsubishi Kasei Co., Ltd. Novalex 7025A

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

[0031]

INDUSTRIAL APPLICABILITY The novel oxyalkylene ether of the present invention is an alkylene oxide adduct of a phenol / divinylbenzene addition polymer, and is useful as an antistatic agent for kneading a molding resin or fiber and a hydrophilicity-imparting agent. Is.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09K 3/16 102 C09K 3/16 102 (56) Reference JP-A 61-145223 (JP, A) ) JP-A-61-145224 (JP, A) JP-A-61-145255 (JP, A) JP-A-61-296024 (JP, A) JP-A-62-45546 (JP, A) JP-A-59- 58019 (JP, A)

Claims (7)

(57) [Claims] 1. An oxyalkylene ether of a phenol / divinylbenzene addition polymer represented by the following general formula (1). (In the above formula, Ar is a phenol residue, Ph is a phenylene group, Q is an alkylene group having 2 to 4 carbon atoms, and m is 1 to 40.
, N is an integer of 0 to 15, m + 2 n may be the same or different, and the sum of m + 2 n is 1 to 500.
Is. ) 2. The phenol is m-and / or p.
An oxyalkylene ether according to claim 1, which is cresol, hydroquinone, nonylphenol or bisphenol A. 3. The oxyalkylene ether according to claim 1, wherein the phenol-divinylbenzene addition polymer has a weight average molecular weight of 1,000 to 10,000. 4. The oxyalkylene ether according to claim 1, wherein the phenol / divinylbenzene addition polymer is linear. 5. The oxyalkylene content in the oxyalkylene ether is 10 to 95% by weight.
An oxyalkylene ether according to any one of 1. 6. An antistatic agent for a resin, comprising the oxyalkylene ether according to claim 1. 7. ABS, polyester, polystyrene,
An antistatic resin composition comprising a resin selected from the group consisting of polycarbonate, polyurethane, polyarylate, polyphenylene oxide, polysulfone and polyethersulfone, and the antistatic agent according to claim 6.