KR0173038B1 - Quaternary ammonium, antistatic compound - Google Patents

Abstract

The present invention relates to a novel antistatic polymerizable hydroxy alkyl morpholinium salt having excellent antistatic property and fouling resistance, and a photocurable resin composition containing the same, (A) an acrylic prepolymer having at least one acrylic group, ( B) at least one hydroxyl group, unsaturated group and morpholinium salt in the molecule, as a compound represented by a monofunctional to polyfunctional acrylic monomer or vinyl ether monomer, (C) photoinitiator and (D) the following general formula (I) It relates to a photocurable resin composition composed of a reactive antistatic agent having a.

Wherein R ₁ is hydrogen or methyl group, n is an integer from 1 to 6, R ₂ is hydrogen or methyl group, R ₃ is hydrogen, methyl or ethyl, X corresponds to monovalent inorganic acid group, organic acid group or inorganic acid or organic acid It's an equivalent.

Description

Antistatic Polymeric Hydroxy Alkyl Morpholinium Salt

The present invention relates to a photocurable resin composition having excellent antistatic property and fouling resistance, and more particularly, to a new antistatic polymerizable hydroxy alkyl morpholinium salt having permanent antistatic property and excellent fouling resistance and containing the same It relates to a photocurable resin composition.

In general, battery electronic devices, home appliances, and precision electronic components used in such products are housed in a case made of a light plastic. Since plastics have high insulation resistance, they are prone to static electricity, and they are adsorbed by dirt in the air. There is this. In addition, dust and static electricity may cause the electronic components to malfunction. Therefore, an anti-static hole is required. Accordingly, the conventional electronic component housing has been processed to prevent static electricity.

Generally, the antistatic property is imparted to thermoplastic resins, including (1) a method of putting an antistatic agent inside (additive type), (2) a method of applying an antistatic agent to a surface, and (3) a silicone-based compound or a surface material (plasma). The above methods are excellent in antistatic effect, but the effect is lost due to water washing or friction, and thus the durability is low.

Recently, a new method has been attempted to give an antistatic effect to a film using a photocurable resin. That is, the monomer and oligomer containing a functional group capable of exhibiting an antistatic effect is cured as a copolymer or a reactive antistatic agent having a specific quaternary ammonium base is introduced into the resin composition to impart a permanent antistatic effect. European Patent No. 541,289, Japanese Patent Application Laid-Open No. 50-98,048, Radtech Asia Magazine 93, p. 492, and Korean Patent Application No. 94-24338. However, such a method provides a permanent antistatic effect, but is about 10 ^12-13 Ω / □, in particular, the compatibility with the photocurable paint is lowered, which causes the problem of precipitation of an antistatic monomer during operation. There is no antistatic agent that can have good properties and exhibit permanent antistatic properties.

The present inventors have diligently studied the phenomenon related to the above-mentioned problems, and as a result, the coating film obtained by UV-curing a coating excellent in compatibility with an acrylic oligomer and an acrylic diluent by using a new antistatic agent monomer as a secondary component has excellent permanent antistatic properties and other comprehensive physical properties. It was found that the present invention was completed based on this.

Accordingly, it is an object of the present invention to provide a novel antistatic agent which, unlike conventional permanent antistatic agents, not only improves the antistatic effect but also improves the stain resistance of the resin and is excellent in compatibility with the photocurable paint.

Still another object of the present invention is to provide a photocurable resin composition containing the antistatic agent as a secondary component and an acrylic oligomer and a monomer as main components.

The polymerizable hydroxy alkyl morpholinium salt which is an antistatic agent of the present invention for achieving the above object is represented by the following formula (I).

Wherein R ₁ is hydrogen or methyl group, n is an integer from 1 to 6, R ₂ is hydrogen or methyl group, R ₃ is hydrogen, methyl or ethyl, X corresponds to monovalent inorganic acid group, organic acid group or inorganic acid or organic acid It's an equivalent.

Photocurable resin composition for achieving another object of the present invention

(A) an acrylic prepolymer having at least one acrylic group,

(B) mono- or polyfunctional acrylic monomers or vinyl ether monomers;

(C) photoinitiators, and

(D) A compound represented by the above general formula (I), preferably composed of a ultraviolet reactive antistatic agent represented by the above general formula (I) having a morpholinium base while having at least one or more hydroxyl and unsaturated groups in the molecule.

Hereinafter, the present invention will be described in more detail.

The novel antistatic agent of the present invention, once cured, does not easily fall off in water washing or abrasion, and can not only impart permanent antistatic effect, but also has excellent compatibility with prepolymers and monomers. The antistatic effect is exhibited without lowering.

The antistatic agent of this invention is acryloyloxypropylene-methylmorpholinium methyl sulfate, acryloyloxy propylene-ethylmorpholinium ethyl sulfate, and acryloyloxy propylene-ethylmol represented by said Formula (I) More preferred are porinium tosylate and the like.

On the other hand, as the prepolymer (a) used in the composition of the present invention as a monofunctional to polyfunctional acrylic resin having at least one or more acrylic groups, for example, polyester acrylate, urethane acrylate or epoxy acrylate Etc. are preferable, and the trade name KR 3000H and the like may be used. The amount used is preferably 40 to 60% by weight based on the final product.

Further, the monomer of (b) used in the present invention is an acrylic or vinyl ether monomer, and as the acrylic, a monofunctional to polyfunctional monomer is preferable, and hydroxyethyl acrylate (HEA) and hydroxyethyl Methacrylate (HEMA), 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), and the like. Butanediol monovinyl ether, 1, 4- cyclohexane dimethanol monovinyl ether, triethylene glycol divinyl ether, and the like. The amount is preferably 30 to 50% by weight based on the final product.

Examples of the component (C) include 1-hydroxy cyclohexylphenyl ketone and α-α-dimethoxy-α'-hydroxy acetophenone as free radical-type photoinitiators. Trade names Irgacure 184 or Darocur 1173. The amount used is preferably 2 to 7% by weight based on the final product, if less than 2% by weight of the unreacted material is generated, the physical properties are lowered, if more than 7% by weight unreacted initiator remains and the weather resistance is lowered. In addition, according to the present invention, since the resin casting of the present invention can be crosslinked by an electron beam without using the photoinitiator, this will also fall within the scope of the present invention.

The amount of the reactive antistatic agent added to the composition of the present invention is 1 to 20% by weight, preferably 3 to 12% by weight based on the total product.

If the added amount is less than 1% by weight, a good antistatic effect cannot be imparted. If it is more than 20% by weight, the overall physical properties of the coating film tend to be greatly reduced, which is not preferable. In general, it is preferable to use about 3 to 12% by weight, in which case the surface resistance is from 10 ¹¹ to 10 ⁶ kPa.

As described above, the ultraviolet curable coating of the present invention exhibits an antistatic effect because it is a complex property of a reactive antistatic agent having a hydroxyl group and a morpholinium base in one molecule used in the present invention. Not only do not drop easily, but also impart a permanent antistatic effect, and excellent compatibility with the prepolymer and other monomers, it is possible to express the antistatic effect without lowering the various physical properties of the resin, such as excellent effects Has

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the following examples do not limit the scope of the present invention.

Example 1

Preparation of 2-hydroxy-3-methacryloyloxy propylene-methyl morpholinium methyl sulfate.

Into a three-necked flask equipped with a thermometer, a reflux cooler, and a dropping funnel, 22.93 g (0.1 mol) of magnetic bar and 2-hydroxy-3-methacryloyl propyl morpholine were stirred, and 40 g of hydroxy propyl acrylate was added thereto. 12.6 g (0.1 mol) of dimethyl sulfate was added dropwise at 50 ° C. over 20 minutes. After completion of the dropwise addition, the mixture was aged for 1 hour to obtain a liquid morpholinium salt. NMR analysis confirmed the structure.

H nmr (300MHZ, CDCl ₃ )

6.2 (S, 1H), 5.65 (S, 1H), 3.5 ~ 4.02 (m, 20H), 1.95 (S, 3H)

Example 2

The components of Table 1 below were stirred and mixed in a conventional manner.

As the antistatic agent, the reactive compound synthesized in Example 1 was used, and as the oligomer, the photoinitiator and the additive, KR3000H from Korea Chemical Industries, UVICURE 204 from Miwon Corporation and BYK 307 from BYK were used as trade names. The mixture was coated on a vinyl chloride resin and a glass plate with a thickness of about 20 μm and 10 μm using S07 and S44 wire bar cottas and UV cured.

Comparative Example 1

Preparation of Acryloyloxypropyl Triethylammonium Methyl Sulfate

Into a three-necked flask, equipped with a magnetic bar, a thermometer, and a cooler, 18.5 g (0.1 mol) of acryloyloxypropyl trimethylamine was added thereto, 40 g of hydroxy acrylate was added thereto, and the temperature was raised to 40 ° C. while stirring. 12.6 g of dimethyl sulfate. (0.1 mol) was added dropwise. After completion of the dropwise addition, the mixture was aged for 1 hour to obtain a liquid quaternary ammonium salt.

Comparative Example 2

Methacryloyloxyethyl trimethylammonium methyl sulfate

Magnetic bar and thermometer were attached to a three-necked flask, and 11.7 g of 2- (dimethylamino) ethyl methacrylate was added thereto, followed by cooling, followed by stirring for 30 minutes with 9.46 g of dimethyl sulfate (crystals began to precipitate during the dropwise addition). ). 500 ml of normal hexane was added to the precipitated crystals, followed by stirring. After filtration, 20.5 g of a white solid compound having a quaternary ammonium base was obtained (molecular weight: 283.36).

Example 3

The components in Table 2 below were stirred and mixed in a conventional manner.

Among the components of Table 2, the same procedure as in Example 2 was carried out except that the product name Rapicure HBVE of ISP Corporation and Irgacure 261 of Ciba-Gay Co. were used as the cationic photoinitiator.

Comparative Example 3

It carried out similarly to Example 2 except using the reactive antistatic agent of the comparative example 1 instead of the reactive antistatic agent of Example 1 as an antistatic agent.

[Comparative Example 4]

It carried out similarly to Example 2 except having used the reactive antistatic agent of the comparative example 2 instead of the reactive antistatic agent of Example 1 as an antistatic agent.

[Comparative Example 5]

It was carried out in the same manner as in Example 2 except that the amino acid system (BYK-ES80), which is a non-reactive antistatic agent, was used instead of the reactive antistatic agent of Example 1 as an antistatic agent.

[Test Example 1]

The surface resistance of the coating on the products of Examples 2 and 3 and Comparative Examples 2 to 5 was measured by using an ultra-insulation resistance meter at 25 ° C. and a humidity of 65% at a voltage of 500 V for 1 minute. Measured. The results are shown in Table 3 below.

[Test Example 2]

The same operation was repeated except that the surface of the coating was washed with water in Test Example 1. After the anti-static effect (Table 3) was evaluated after the water treatment, all of the antistatic effect except for the additive type antistatic agent of Comparative Example 5 was proved permanent.

※ After staining with oil-based magic, wipe it with a tissue and mark it as ◎ if there is no measurement mark.If there is a trace, mark ○, and the adhesive force is 1mm wide. Measure. Surface resistance was measured by the instrument.

It can be seen from the above examples and comparative examples that the resin composition of the present invention is an excellent photocurable resin composition exhibiting permanent antistatic properties.

Claims (3)

A reactive antistatic agent having a morpholinium salt represented by the following general formula (I). Wherein R ₁ is hydrogen or methyl group, n is an integer from 1 to 6, R ₂ is hydrogen or methyl group, R ₃ is hydrogen, methyl or ethyl, X corresponds to monovalent inorganic acid group, organic acid group or inorganic acid or organic acid It's an equivalent. The reactive antistatic agent according to claim 1, having a morpholinium salt represented by the general formula (I) having a quaternary ammonium base while having at least one hydroxyl group and an unsaturated group in a molecule. The compound represented by the formula (I) is acryloyloxypropylene-methylmorpholinium methyl sulfate, acryloyloxy propylene-ethylmorpholinium ethyl sulfate or acryloyloxy propylene-ethyl A reactive antistatic agent having a morpholinium salt, characterized in that it is morpholinium tosylate.