JPS62164748A - Acrylic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having an excellent antistatic effect, consisting of an acrylic resin, a specified copolymer, a metal salt capable of forming a solid solution with said copolymer and an org. solvent. CONSTITUTION:20-80wt% (meth)acrylic ester is copolymerized with 80-20wt% monomer having a copolymerizable unsaturated bond and 4-500 ethylene oxide groups, represented by formula I, II or III (wherein R1, R2 and R3 are each H, a 1-4C alkyl; X is H, a 1-9C alkyl, phenyl, SO3M, SO2M, PO3, M3, or a group of formula IV, V or VI; R4, R5 and R6 are each H, a 1-9C alkyl; M is H, Li, Na or K; 4<=m+n<=500; Y is H, a 1-40C alkyl, a 3-6C cycloalkyl, phenyl or a group of formula VII; 4<=p+q<=500) to obtain a copolymer (B) 100pts.wt. acrylic resin (A) is blended with 5-100pts.wt. component B, 0.2-20pts. wt. metal salt (C) capable of forming a solid solution with the component B (e.g., KClO4) and 0-20pts.wt. org. solvent (D) for the component C (e.g., triethylene glycol).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a transparent resin composition having an antistatic effect.

[Conventional technology]

Generally, plastic has a high electrical resistance and is easily charged with electricity due to friction, etc., which attracts dirt and dust, which can damage the appearance and cause electrical and electronic equipment to malfunction or break down.

In order to reduce the chargeability of such easily charged plastics, it is known to apply an antistatic agent or to knead it into the plastic. Surfactants and silicone compounds are generally known as antistatic agents for coating.

[Problem that the invention seeks to solve]

However, the surfactant is easily removed by washing, and it is difficult to expect a long-term antistatic effect.

Although silicon-based compounds can be expected to have a fairly good antistatic effect, they are not only difficult to control coating conditions, but also have poor work efficiency and are disadvantageous in terms of cost.

When an antistatic agent is internally kneaded, the antistatic effect is achieved by the antistatic agent seeping out onto the surface, so the effect is drastically reduced by washing with water or friction, and it takes a long time to recover the antistatic effect.

In addition, in both of the above methods, water in the air is adsorbed onto the surface, increasing the ionic conductivity of the resin surface and exerting an antistatic effect, so the presence of water is essential and low In a humid environment, there are problems such as a decrease in antistatic effect.

The present invention was made in order to solve the problems of the conventional technology as described above, and it is an acrylic resin composition that maintains a good antistatic effect even in a low humidity environment and whose antistatic properties do not deteriorate when washed. The purpose is to provide something.

[Means to solve problems]

The present invention is capable of copolymerizing with 100 parts by weight of acrylic resin, 20 to 80% by weight of one or more monomers selected from methacrylic esters and acrylic esters, and 4 to 500 alkylene oxide groups. one or more monomers selected from monomers having unsaturated bonds 20-8
5 to 100 parts by weight of a copolymer obtained by copolymerizing 0% concavity, 0.2 to 20 parts by weight of a metal salt dissolved in the copolymer, and θ to 20 parts by weight of an organic solvent for the metal salt. The present invention relates to an acrylic resin composition containing the following.

[For production]

In the acrylic resin composition of the present invention, the metal salt is dissolved in the acrylic resin composition and ionically dissociated, and when an electric field is applied, these ions move through the resin composition and the electric field is suppressed. It shows antistatic effect by trying to neutralize it. The polyalkylene oxide monomer in the copolymer has the effect of ionically dissociating the metal salt dissolved in solid solution under non-aqueous conditions, and therefore the resin composition has a stable antistatic effect even under low humidity conditions, regardless of moisture absorption. shows. Furthermore, in order to blend the metal salt more uniformly, an organic solvent that dissolves the metal salt may be mixed. If the metal salt is uniformly blended, the antistatic effect will be improved, but since the organic solvent acts as a plasticizer, the heat distortion temperature of the resin composition will be slightly lowered.

The one or more monomers selected from methacrylic esters and acrylic esters in the copolymer are selected so that the copolymer has compatibility with the acrylic resin. Therefore, the copolymer is uniformly dispersed in the acrylic resin and does not impair the good transparency of the acrylic resin.

〔Example〕

The acrylic resin composition of the present invention contains, based on 100 parts by weight of the acrylic resin, 20 to 80% by weight of one or more monomers selected from methacrylic esters and acrylic esters and 4 to 500 alkylene oxide groups. has
5 to 100 parts by weight of a copolymer obtained by copolymerizing 20 to 80% by weight of one or more monomers selected from monomers having copolymerizable unsaturated bonds; 0.2 to 20 parts by weight of a solid-dissolved metal salt and 0 to 2 parts of an organic solvent for the metal salt
It can be obtained by blending 0 parts by weight.

Examples of the acrylic resin used in the present invention include Acrypet (manufactured by Mitsubishi Rayon), Parapet (manufactured by Kyowa Gas Chemical), Chillpet (manufactured by Asahi Kasei), and Sumipex (manufactured by Asahi Kasei).
Commercially available materials such as those manufactured by Custom Chemical Industry Co., Ltd.) can be used, but the material is not limited to these, and other acrylic resins can also be used.

The copolymer used in the present invention has 20 to 80% by weight of one or more monomers selected from methacrylic esters and acrylic esters and 4 to 500 alkylene oxide groups, and has copolymerizable inorganic compounds. It can be obtained by copolymerizing 20 to 80% by weight of one or more monomers selected from monomers having saturated bonds.

The methacrylic ester and acrylic ester are selected so that their polymers are compatible with the acrylic resin, such as methyl methacrylate, ethyl methacrylate, 1ln-butyl methacrylate, and t-methacrylate.
Butyl, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, alkyl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid, methacrylic F [? 2- and droxyethyl, methacrylic M2-hydro+3.7゛L, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, dimethylaminoethyl methacrylate methyl chloride salt, methyl acrylate, etc. methacrylic acid ester; one or more types of acrylic esters corresponding to methacrylic esters such as ethyl acrylate and acrylic acid can be used, but of course, in addition to this, it is possible to use other polymers that are compatible with the acrylic resin. One or more monolayers can be used.

The monomer having the alkylene oxide group and having a copolymerizable unsaturated bond is represented by the general formula (1) shown below.
), (1) or (9) is preferably used.

(In the formula, R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a phenyl group, SO, H, 802M, PO, M2, CH2
CHCOOH.

represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, H represents a hydrogen atom, Li, Ha, or Ni. R2 and R3 represent the same or different hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. (2) and n represent integers satisfying 4≦l+n≦500. Y is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, or p and q are 4≦I)+Q≦50
Indicates an integer that satisfies 0. ) (wherein R1, Il2, R3,
In the formula, R5, R2, R3, X, Y SII and n
is the same as that defined in the above general formula [I)) Among the monomers represented by the above general formulas (1) to 1, at least one of R2 and R3 is H, and 4 or more ethylene oxide Those having groups are particularly preferred because they have a large ion dissociation ability. Of course, the general formula (I) ~
Other than the single solid represented by the circle, similar monomers that have copolymerizable unsaturated bonds and polyalkylene oxide groups, are nonaqueous, and have ionic dissociation power can be used.

If the number of alkylene oxide groups in the monomer having an alkylene oxide group and a copolymerizable unsaturated bond as described above is less than 4, the ionic dissociation ability will be small and the antistatic It is difficult to assign gender, and 5
If there are more than 00 pieces, the transparency of the resin composition is likely to be impaired, so 4 to 500 pieces are required, especially 9 to 500 pieces.
When the number is 50, it is preferable because it provides both excellent ion dissociation ability and transparency.

The monomer having the alkylene oxide group and having a copolymerizable unsaturated bond has a concentration of 20 to 80% during the copolymerization.
It is preferable that weight X is included. If the content is 20% by weight without vortex, the ion dissociation ability is too small, 80% by weight! If it exceeds X, it is not preferable because it loses compatibility with the acrylic resin and impairs the transparency of the resin composition.

The amount of the copolymer thus obtained is preferably in the range of 5 to 100 parts by weight based on 100 parts by weight of the acrylic resin. If the amount of the copolymer is less than 5 parts by weight, the improvement in conductivity due to ionic dissociation will be small, and if it exceeds 100 parts by weight, the good mechanical properties of the acrylic resin will be impaired.

The metal salt dissolved in the copolymer gives conductivity to the resin,
These are ingredients to prevent static electricity, such as lithium perchlorate, sodium perchlorate, potassium perchlorate,
Cesium perchlorate, lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, cesium thiocyanate, lithium borofluoride, sodium borofluoride,
Potassium borofluoride, lithium bromide, lithium iodide,
Sodium iodide, potassium iodide, lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, lithium trifluoroacetate, sodium trifluoroacetate, potassium trifluoroacetate, lithium trifluoromethanesulfonate, trifluoromethanesulfone Conventionally used materials such as sodium acid, potassium trifluoromethanesulfonate, lithium tetraphenylborate, sodium tetraphenylborate, and potassium tetraphenylborate can be used alone or in combination of two or more.

If the metal salt dissolved in the copolymer is less than 0.2 parts by weight based on 100 parts by weight of the acrylic resin, there will be little improvement in conductivity and the antistatic effect will be small, and if it exceeds 20 parts by weight, crystallization will occur. is likely to precipitate, impairing the transparency of the resin composition and making it brittle, so it is preferably blended in an amount of 0.2 to 20 parts by weight.

Examples of the organic solvent for the metal salt include glymes such as triethylene glycol, dimethyl ether, tetraethylene glycol, and dimethyl ether; polyethylene glycol, polypropylene glycol, propylene carbonate, ethylene carbonate, dimethylformamide, middle formamide, dimethylacetamide, tomethylpyrrolidone, and tetraethylene glycol; Methylurea, hexamethylphosphoramide, dimethyl sulfoxide, acetonitrile, sulfolane, etc. are used, and these may be used alone or in combination of two or more. The blending ratio of the organic solvent is preferably 20 parts by weight or less based on 100 parts by weight of the acrylic resin. If the blending ratio exceeds 20 parts by weight, the heat deformation temperature of the resin composition decreases and the value as a general plastic material decreases, which is not preferable.

Although the acrylic resin composition of the present invention thus obtained has excellent antistatic properties and transparency, it cannot be processed by ordinary molding methods such as injection molding, extrusion molding, compression molding, or vacuum forming. can be used.

Next, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

Example 1 60 parts of methyl methacrylate, the average number of ethylene oxide groups being about 2, was placed in a 11 glass flask equipped with a stirring blade.
A solution consisting of 40 parts by weight of three methoxypolyethylene glycol methacrylates, 100 parts by weight of methanol, and 2 parts by weight of α,α°-azoisobisbutyronitrile was charged and stirred at 62° C. for 5 hours. Thereafter, methanol was removed and vacuum drying was performed at 80° C. for 16 hours to obtain a copolymer.

30 parts by weight of lithium perchlorate was kneaded with 100 parts by weight of the above-obtained copolymer at 100° C. for 5 minutes using a kneader.

Next, 25 parts by weight of the above-obtained mixed material was heated to 200°C and kneaded using a kneader to 100 parts by weight of acrylic resin (Mitsubishi Rayon ■, Acryvet VHK).
Press molded at 400 kg/cm2 at ℃, thickness 1.51
A test piece was prepared. The antistatic property of this test piece was evaluated by measuring the half-life of the charging voltage using a static honest meter (manufactured by Shishido Shokai). The results are shown in Table 1. Note that the measurement conditions are as follows.

Applied voltage 10000V Application time: 1 minute Table rotation speed: 1300rpi Measurement temperature: 25℃ Measurement humidity 40-55XRH Next, the transparency of the test piece was evaluated by light transmittance.

The measurement method was performed according to the method of ASTH 01003. The results are shown in Table 1.

Example 2 A test piece was prepared in the same manner as in Example 1 except that sodium perchlorate was used instead of lithium perchlorate as the metal salt, and the antistatic property and transparency of the test piece were determined in the same manner as in Example 1. The gender was evaluated. The results are shown in Table 1.

Example 3 A test piece was prepared in the same manner as in Example 1 except that sodium thiocyanate was used instead of lithium perchlorate as the metal salt, and the antistatic property and transparency of the test piece were determined in the same manner as in Example 1. was evaluated. The results are shown in Table 1.

Example 4 A test piece was prepared in the same manner as in Example 1 except that potassium thiocyanate was used instead of lithium perchlorate as the metal salt, and the antistatic property and transparency of the test piece were determined in the same manner as in Example 1. was evaluated. The results are shown in Table 1.

Example 5 Same as Example 1 except that methoxypolyethylene glycol methacrylate having an average number of ethylene oxide groups of about 9 was used instead of methoxypolyethylene glycol methacrylate having an average number of ethylene oxide groups of about 23. A copolymer was prepared, a test piece was prepared, and the antistatic properties and transparency were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 A test piece was prepared in the same manner as in Example 1 using only an acrylic resin (manufactured by Mitsubishi Rayon ■, Acrybet VH), and the antistatic property and transparency were evaluated. The results are shown in Table 1.

Comparative Example 2 25 parts by weight of a copolymer prepared in the same manner as in Example 1 and 10 parts of acrylic resin (Mitsubishi Rayon Co., Ltd., Acryvet VH)
A test piece containing no metal salt was prepared by kneading 0 parts by weight in the same manner as in Example 1, and the antistatic properties and transparency were evaluated. The results are shown in Table 1.

Comparative Example 3 A test piece was prepared by adding only 2 parts by weight of lithium perchlorate to 100 parts by weight of acrylic resin (manufactured by Mitsubishi Rayon M, Acryvet VH) and kneading it in the same manner as in Example 1. Transparency was evaluated. The results are shown in Table 1.

Table 1 Example 6 Same as Example 1 except that the blending ratio of methyl methacrylate was 40 parts by weight and the blending ratio of methoxypolyethylene glycol methacrylate having an average number of ethylene oxide groups of about 23 was 60 parts by weight. A copolymer was prepared and a test piece was produced in the same manner as in Example 1. Next, antistatic properties and transparency were evaluated in the same manner as in Example 1. The second result is
Shown in the table.

Example 7 A copolymer was produced in the same manner as in Example 1, except that the blending ratio of methyl methacrylate was 70 parts by weight, and the blending ratio of methoxypolyethylene glycol methacrylate having an average number of ethylene oxide groups of about 23 was 30 parts by weight. A test piece was prepared in the same manner as in Example 1. Next, antistatic properties and transparency were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 4 A copolymer was prepared in the same manner as in Example 1, except that the blending ratio of methyl methacrylate was 10 parts by weight and 90 parts by weight of methoxypolyethylene glycol methacrylate having an average number of ethylene oxide groups of about 23. A test piece was prepared. Next, antistatic properties and transparency were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 5 A copolymer was prepared in the same manner as in Example 1, except that the blending ratio of methyl methacrylate was 90 parts by weight and 10 parts by weight of methoxypolyethylene glycol methacrylate having an average number of ethylene oxide groups of about 23. , a test piece was prepared. Next, antistatic properties and transparency were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Table 2 Example 8 A copolymer was prepared in the same manner as in Example 1, and then a solution was prepared by dissolving 30 parts by weight of lithium perchlorate in 100 parts by weight of tetraethylene glycol dimethyl ether.

Add 30 parts by weight of this copolymer and 5 parts by weight of the resulting solution to acrylic resin (Mitsubishi Rayon special Acryvet VH).
100 parts by weight was kneaded in the same manner as in Example 1 to prepare a test piece. The antistatic property and transparency of the obtained test piece were evaluated in the same manner as in Example 1. The results are shown in Table 3.

Example 9 After preparing a copolymer in the same manner as in Example 1, 35 parts by weight of lithium perchlorate was mixed with 100 parts by weight of propylene carbonate.
A solution containing parts by weight was prepared. 30 parts by weight of this copolymer and 3 parts by weight of the solution were kneaded with 100 parts by weight of an acrylic resin (Mitsubishi Rayon-type Acrybet VH) in the same manner as in Example 1 to prepare a test piece.

The antistatic property and transparency of the obtained test piece were evaluated in the same manner as in Example 1. The results are shown in Table 3.

Example 10 A copolymer was prepared in the same manner as in Example 1, and then a solution was prepared by dissolving 30 parts by weight of lithium perchlorate in 100 parts by weight of sulfolane. This copolymer 30 overlapping part and solution 5
Parts by weight were kneaded to prepare test pieces.

The antistatic properties and transparency of the obtained test pieces were evaluated in the same manner as in Example 1. The results are shown in Table 3.

Example 11 The composition of the copolymerization solution was 40 parts by weight of methyl methacrylate, 20 parts by weight of methacrylic acid, 40 parts by weight of methoxypolyethylene glycol methacrylate having an average number of ethylene oxide groups of about 23, 100 parts by weight of methanol,
A copolymer was prepared in the same manner as in Example 1 using 1 part of α,α'-azoisobisbutyronitrile double, and a test piece was prepared. Next, antistatic properties and transparency were evaluated in the same manner as in Example 1. The results are shown in Table 3.

Example 12 The composition of the copolymerization solution was as follows: 40 parts by weight of methyl methacrylate, 20 parts by weight of dimethylaminoethyl methacrylate, 4GIi parts of methoxypolyethylene glycol methacrylate having an average number of ethylene oxide groups of about 23, and 10011 parts of methanol! A copolymer was prepared in the same manner as in Example 1 using 1 part by weight and 2 parts by weight of α,α°-azoisobisbutyronitrile, and a test piece was produced. Next, antistatic properties and transparency were evaluated in the same manner as in Example 1. The results are shown in Table 3.

As can be seen from the results in Table 3 and above, the acrylic resin composition of the present invention has an excellent half-life of charging voltage of 1.0 seconds or less, and also has an extremely high light transmittance of 85% or more. It turns out that it is excellent.

[Effects of the Invention] The acrylic resin composition of the present invention has the function of solidly dissolving metal salts, dissociating ions, and preventing electrification by ionic conduction in a non-aqueous system, and can be used in a low-humidity environment. It exhibits excellent antistatic properties even when exposed to static electricity, and its antistatic properties do not deteriorate even after washing, making it suitable for electronic and electrical equipment parts, building materials, interior goods, etc. used in such environments. It can be used for.

Furthermore, since the acrylic resin composition of the present invention has excellent light transmittance, it can be suitably used for, for example, indicator covers, IC storage containers, cathode ray tube front covers, lighting covers, audio equipment covers, and the like.

Agent Masuo Oiwa Procedural amendment (voluntary) May 26, 1985

Claims (1)

[Claims] (1) 1 selected from methacrylic ester and acrylic ester based on 100 parts by weight of acrylic resin
20 to 80% by weight of more than one type of monomer and 20 to 80% of one or more monomers selected from monomers having 4 to 500 alkylene oxide groups and copolymerizable unsaturated bonds.
5 to 100 parts by weight of a copolymer obtained by copolymerizing % by weight, 0.2 to 20 parts by weight of a metal salt dissolved in the copolymer, and 0 to 20 parts by weight of an organic solvent for the metal salt. Acrylic resin composition.