JPH0987549A - Antistatic coating composition and antistatic molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic molding excellent in adhesion and scratch resistance by coating a molding with a coating agent containing a lactone- modified polyvinyl alcohol and a radical-polymerizable monomer and irradiating the coating agent with an actinic radiation. SOLUTION: This antistatic coating composition is prepared by mixing 100 pts.wt. lactone-modified polyvinyl alcohol (A) represented by the formula (wherein X, Y and Z are molar percentages and are in the ranges: 0<=X<=95, 0<=Y<=30 and 5<=Z<=100, provided that X+Y+Z=100, the bonding of two components is random; R<1> is a 2-10C linear alkylene; R<2> is AH or acetyl; and (n) is the average number of moles of the lactone entered into the addition reaction and is in the range: 1<=n<=10) with 10-1,000 pts.wt. radical-polymerizable monomer (B) and 0-1,000 pts.wt. organic solvent (C). Component A is prepared by melt-kneading a polyvinyl alcohol and a lactone monomer in the presence of a catalyst. Component B is represented by an acrylic monomer. This coating agent is applied to artificial leathers, textile products, components of OA machines and of household electric appliances, and the applied agent is irradiated with an actinic radiation to obtain good-quality antistatic moldings.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic coating composition for antistatic processing, a molded article subjected to antistatic processing, and a method for producing the molded article.
More specifically, automobile seats, sofas, shoe soles, artificial leather products such as gloves, flooring materials for construction, building materials such as synthetic resin tiles, textiles, clothes, hats, skirts, stockings, blankets, jutan, slippers, etc. TECHNICAL FIELD The present invention relates to a coating composition used for antistatic processing of textile / nonwoven products, copiers, facsimiles, computers, printers, refrigerators, televisions, and other OA equipment / home appliance parts, automobile parts, and antistatic processed products. .

[0002]

Plastic and rubber materials are used in a wide variety of fields due to their excellent properties. However, since most of these materials are hydrophobic, static electricity is likely to be generated, and this static electricity causes disadvantages such as discomfort to users, malfunction of the device, and dust adhesion. Have For this reason, many products that have been subjected to antistatic processing have been developed, but at present, few products have a good balance between the antistatic effect and the price.

[0003]

Although there are many techniques for coating a plastic material with an antistatic agent,
The major drawback is that the antistatic agent falls off and the effect does not last long.

[0004]

Means for Solving the Problems The present inventor has blended a lactone-modified polyvinyl alcohol (A), which is an antistatic agent, and a radical-polymerizable monomer (B), applied the mixture to a molded article, and then activated energy rays. By irradiating UV light to form a cured coating layer, not only the antistatic agent does not fall off, but also the adhesion to the molded product, toughness, hardness, scratch resistance, chemical resistance, water resistance, etc. It was found that a molded product having an excellent antistatic coating layer can be obtained, and the present invention has been completed.

That is, according to the present invention, 100 parts by weight of the lactone-modified polyvinyl alcohol (A) represented by the following general formula (1) and the radical-polymerizable monomer (B) are used.
10 to 1000 parts by weight and organic solvent (C) 0 to 100
An antistatic coating composition consisting of 0 parts by weight is provided.

[0006]

Embedded image

Further, according to the present invention, the antistatic coating composition is obtained by applying or impregnating a molding with the above-mentioned antistatic coating composition and then irradiating the molding with an active energy ray. A processed compact is provided.

Further, according to the present invention, the above-mentioned antistatic coating composition is applied to or impregnated into a molded body, and then the molded body is irradiated with active energy rays. Provided is a method for producing an anti-molded compact.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION First, an antistatic coating composition of the present invention comprising a lactone-modified polyvinyl alcohol (A), a radically polymerizable monomer (B) and an organic solvent (C) which is an optional component will be explained. To do.

The lactone-modified polyvinyl alcohol (A) has a structure represented by the above general formula (1). Preferred ranges of X, Y, Z and n in the general formula (1) are 30 ≦ X ≦ 80 and 0 ≦ Y ≦ 2, respectively.
0, 20 ≦ Z ≦ 70, and 1.5 ≦ n ≦ 5.0. If the proportion of the lactone component in the two components (polyvinyl alcohol component and lactone component) constituting the lactone-modified polyvinyl alcohol (A) increases too much, the antistatic effect decreases, while if the proportion of the polyvinyl alcohol component increases too much. However, it is not preferable because the adhesion to the hydrophobic molded article is reduced.

The degree of polymerization of oxyethylene units in the main chain of lactone-modified polyvinyl alcohol is usually 1
The range is from 00 to 2000, preferably from 300 to 1000.

If the degree of polymerization is less than 100, it is difficult to produce, and thus it is not preferable. On the contrary, if the degree of polymerization is more than 2000, the viscosity of the antistatic coating composition is increased and the coating is difficult. It is not preferable because it becomes difficult and it becomes uneconomical to use a large amount of organic solvent.

R ¹ in the formula is a linear alkylene group having 2 to 10 carbon atoms, and may be substituted with any number (from 2 times to 1 carbon atom of R ¹ ) of methyl group. In particular,
A pentylene group, a pentylene group substituted with a methyl group, a butylene group, an ethylene group and the like are preferable. Especially when ε-caprolactone, which is the most useful lactone monomer industrially, is used for modification, R ¹ is a pentylene group, and this is preferably used.

R ² is basically a hydrogen atom or an acetyl group. The range of the molar composition% of the hydrogen atom or the acetyl group is not particularly limited and can be set by adjusting the production method, production conditions and the like of the lactone-modified polyvinyl alcohol of the present invention.

The lactone-modified polyvinyl alcohol used in the present invention can be obtained by the following production method. That is, polyvinyl alcohol 5 to 95 parts by weight,
95 to 5 parts by weight of lactone monomer (total of 100 parts by weight of both) and 0.001 to 0.1 parts by weight of polymerization catalyst are melt-kneaded at a temperature of 50 to 250 ° C. with respect to 100 parts by weight of both. The mixing ratio of the polyvinyl alcohol, which is the raw material of the lactone-modified polyvinyl alcohol, and the lactone monomer is the optimum mixing ratio within the above-mentioned mixing ratio range in consideration of the functional balance in the intended use of the lactone-modified polyvinyl alcohol. It is preferable.

The polymerization catalyst used for producing the lactone-modified polyvinyl alcohol is a ring-opening addition polymerization catalyst of a lactone monomer. Specific examples include inorganic bases, inorganic acids, organic alkali metal catalysts, tin compounds, titanium compounds, aluminum compounds, zinc compounds, molybdenum compounds and zirconium compounds. Among them, tin compounds and titanium compounds are preferably used in terms of balance of handling easiness, low toxicity, reactivity, non-coloring property, thermal stability and the like.
Specific examples of the tin compound include stannous chloride, stannous octylate, monobutyltin oxide, monobutyltin compounds such as monobutyltin tris (2-ethylhexanate), dibutyltin compounds such as dibutyltin oxide, and titanium compounds. Examples thereof include tetrabutyl titanate and tetra-isopropyl titanate.
These can be used alone or in combination.

The amount of the polymerization catalyst added is 0.001 to 0.1 part by weight, preferably 0.002 to 0.05 part by weight, more preferably 0.005 part by weight, based on 100 parts by weight of the total amount of both raw materials. ~ 0.01 parts by weight. When the amount of the catalyst is 0.
When it is less than 001 parts by weight, the addition polymerization rate of the lactone monomer is slow, and when it is more than 0.1 parts by weight,
The resulting lactone-modified polyvinyl alcohol may be colored or the thermal stability may be deteriorated, which is not preferable. The polymerization temperature is 50 to 250 ° C, preferably 100 to 220 ° C, more preferably 160 to 20 ° C.
It is in the range of 0 ° C. When the temperature is lower than 50 ° C, the addition polymerization rate of the lactone monomer is slow, and when the temperature is higher than 250 ° C, a thermal decomposition reaction of the lactone adduct occurs to cause coloration or decomposition products. Not preferable.

In the method for producing lactone-modified polyvinyl alcohol, a known melt-kneading machine can be used without any problem as a production apparatus for carrying out melt-kneading. Specifically, it is preferable to use a stirring blade type batch kneader, a kneader type kneader, a screw type kneader such as an extruder, a static mixer type kneader, and these devices continuously connected.

Further, in the method for producing the lactone-modified polyvinyl alcohol, the order of addition of the raw materials and the polymerization catalyst and the addition method are not limited at all, but the amount of water contained in the raw materials is 0.5% by weight or less, preferably 0. It is desirable that the amount is 1% by weight or less, and more preferably 0.05% by weight or less.
When the amount of water contained in the raw material exceeds 0.5% by weight, addition polymerization of the lactone monomer from the water occurs and polylactone oligomers are produced, so that the lactone-modified polyvinyl alcohol becomes cloudy or has various functions. It is not preferable because it may decrease.

The lactone-modified polyvinyl alcohol (A) represented by the general formula (1) has a radically polymerizable group introduced therein.
Can also be used. By using this, physical properties such as hardness, scratch resistance, chemical resistance and water resistance of the coating film can be further improved.

The introduction method is not particularly limited, but is a method in which a compound having a radical polymerizable group such as a (meth) acrylic acid derivative is added to a lactone-modified polyvinyl alcohol (a part of the hydroxyl groups in A). Is preferably used.

As the above-mentioned (meth) acrylic acid derivative,
(Meth) acrylic acid, lower ester of (meth) acrylic acid (having 1 to 4 carbon atoms), (meth) acrylic acid halide, glycidyl (meth) acrylate, methacroyl isocyanate, 2- (3-isopropenylphenyl) -2 -Isocyano-propane, 2-isocyanoethyl methacrylate, isopropenyl oxazoline and the like can be exemplified.

Lactone modified polyvinyl alcohol (A)
A part of the hydroxyl groups in the inside is usually 0.1 to 50 of the total number of moles.
%, Preferably about 1 to 20%. If it is less than 0.1%, the effect of the addition reaction is not exhibited, and conversely, if it exceeds 50%, the antistatic property decreases, which is not preferable.

The addition reaction can be carried out by adding these compounds directly to the lactone-modified polyvinyl alcohol (A) or after dissolving or dispersing the lactone-modified polyvinyl alcohol (A) in an organic solvent. In order to suppress the polymerization of the radically polymerizable group, it is preferable to add a polymerization inhibitor or air in the reaction system.

The temperature of the above addition reaction is usually from room temperature to 15
It is in the range of 0 ° C, preferably 60 ° C to 120 ° C. It is not necessary to lower the temperature below room temperature, and it is not preferable at 150 ° C. or higher because the radically polymerizable group may polymerize.

The radically polymerizable monomer (B) in the present invention is a curable monomer represented by a curable acrylic monomer containing a polyfunctional acrylic monomer and a mixture thereof. In some cases, it may contain a radically polymerizable monomer such as a monofunctional acrylic monomer, styrene or acrylonitrile.

Specific examples of the polyfunctional acrylic monomer include ethylene oxide-modified bisphenol A.
(Meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, caprolactone modified dipentaerythritol hexaacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) ) Isocyanurate and mixtures thereof can be mentioned as examples of monofunctional acrylates. The system monomer, methyl (meth)
Acrylate, butyl (meth) acrylate, tert
-Butyl (meth) acrylate, acrylonitrile,
(Styrene) tetrahydrofurfuryl acrylate, 2
Examples thereof include phenoxyethyl acrylate, nonylphenoxypolyethoxylated acrylate, ethyl cellosolve acrylate, isononyl acrylate, isodecyl acrylate, and glycidyl (meth) acrylate.

The proportion of the polyfunctional acrylic monomer in the radical-polymerizable monomer (B) may be any that is sufficient for curing, and is usually 10 to 100 mol%.

Lactone modified polyvinyl alcohol (A)
The addition amount of the radically polymerizable monomer (B) to 100 parts by weight is 10 to 1000 parts by weight, preferably 50 to 100 parts by weight.
The range is 500 parts by weight.

When the amount added is less than 10 parts by weight, the toughness, hardness, scratch resistance and the like of the cured coating layer are significantly reduced, and conversely, when it exceeds 1000 parts by weight, the antistatic effect is reduced, which is not preferable. .

The organic solvent (C) in the present invention is added in an appropriate amount as necessary in order to adjust the viscosity so that the antistatic coating composition can be easily applied to or impregnated into a molded article.
Since the organic solvent is added only for the purpose of adjusting the viscosity, the addition amount is preferably as small as possible.

The organic solvent is preferably one which does not undergo phase separation in the system and has a boiling point of 50 to 200 ° C. under normal pressure so that the antistatic coating composition can be uniformly applied or impregnated.

Specifically, alcohols such as ethyl alcohol, isopropyl alcohol and butyl alcohol,
Examples thereof include esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, aromatic hydrocarbons such as toluene and xylene, and mixed solvents thereof.

Next, the antistatic molded body of the present invention and the method for producing the same will be described. As the molded body to be subjected to the antistatic treatment, a molded body mainly made of a plastic and a rubber material is used. Specifically, automobile seats, sofas, shoe soles, artificial leather products such as gloves, flooring materials for construction, building materials such as synthetic resin tiles, textiles, clothes, hats, skirts, stockings, blankets, jutan, slippers, etc. The textile and non-woven fabric products, copiers, facsimiles, computers, printers, refrigerators, televisions, and other office automation equipment and home appliance parts, automobile parts, and the like.

The antistatically processed molded article of the present invention is obtained by applying or impregnating the above-mentioned antistatic coating composition to a molded article, drying it if necessary, and then irradiating the molded article with active energy rays. To be

The coating method is not particularly limited, and examples thereof include brush, spray coating, dip coating, spin coating,
Examples of the coating method include roll coating and flow coating. The impregnation method is not particularly limited, and the conventional method can be used.

The drying method is also not particularly limited, and it may be naturally dried at room temperature or may be dried by heating.

The active energy ray in the present invention means ultraviolet rays, electron rays, plasma, X-rays, γ rays and the like. When the active energy rays are ultraviolet rays, a photoinitiator, a photoinitiator aid, or a sensitizer such as an acetophenone type, a benzoin type, a benzophenone type, or a thioxanthone type can be used.

In the antistatic coating composition of the present invention, it is possible to add various stabilizers such as a polymerization inhibitor, a heat resistance stabilizer and a light stabilizer, wax, an inorganic filler (filler), a pigment and the like. .

[0040]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[Production Example 1] Polyvinyl alcohol "PVA-4" manufactured by Kuraray Co., Ltd. was placed in a 1-liter glass flask.
03 "(saponification degree 80 mol%, polymerization degree 300) 300 g
And 720 g of ε-caprolactone were charged to 100
By removing 20 g of ε-caprolactone under the condition of 2 ° C and 2 mmHg, the water content in the raw material is 0.01% by weight.
And Next, 0.02 g of stannous chloride as a polymerization catalyst was added, the temperature was raised to 180 ° C., and melt kneading was performed for 5 hours. The amount of ε-caprolactone remaining in the obtained lactone-modified polyvinyl alcohol was 0.13%.

This is a colorless and transparent viscous liquid,
The values of X, Y, Z and n in the general formula (1) were 45, 20, 35 and 2.3, respectively (GPC
And measured by 1 H-NMR).

[Production Example 2] Polyvinyl alcohol "PVA-1" manufactured by Kuraray Co., Ltd. was placed in a 1-liter glass flask.
03 "(saponification degree 99.5 mol%, degree of polymerization 300) 40
0 g, 400 g of ε-caprolactone and 0.02 g of stannous chloride as a polymerization catalyst were charged, the temperature was raised to 180 ° C., and melt kneading was performed for 5 hours. The amount of ε-caprolactone remaining in the obtained lactone-modified polyvinyl alcohol was 0.18%.

This was a very flexible transparent solid, and the values of X, Y, Z and n in the general formula (1) were 74, 0, 26 and 1.5, respectively.

[Production Example 3] 300 g of the lactone-modified polyvinyl alcohol obtained in Production Example 1 was charged into a 1-liter glass flask and the temperature was adjusted to 90 ° C. In addition,
The hydroxyl value of this product was 4.58 mmol / g of resin. Methoxyquinone 0.15 as a polymerization inhibitor
g was added and mixed. 2- (3
20.1 g (0.1 mol) of -isopropenylphenyl) -2-isocyano-propane was added dropwise, and after completion of the addition 1
Stir and mix for hours. This was used as a radically polymerizable group-added lactone-modified polyvinyl alcohol in Example 3.

Example 1 100 parts by weight of the lactone-modified polyvinyl alcohol obtained in Production Example 1 was used as a radical-polymerizable monomer (B), pentaerythritol triacrylate (PETI manufactured by Daicel-VCB Co., Ltd.).
100 parts by weight of A) and 100 parts by weight of 1,6-hexanediol diacrylate were stirred and mixed at room temperature to obtain an antistatic coating composition.

This composition was subjected to polybutylene terephthalate (Polyplastics Co., Ltd.) using a roll coating method.
Made, DURANEX 600FP) sheet (thickness 2.0
mm) on one side.

This sheet was irradiated with an electron beam using an electron beam irradiation device under the conditions of an accelerating voltage of 175 kV and an irradiation dose of 5 MRad to cure the radically polymerizable monomer and form a coating layer (thickness 50 μm). The following test evaluation was performed on this sample. The results are shown in Table 1.

(1) Appearance It is visually evaluated whether the coating layer is uniform without unevenness or cracks. (∘: good, Δ: acceptable, x: bad) (2) Pencil hardness According to JIS K5400. (3) Surface resistivity Super insulation meter S manufactured by Toa Denpa Kogyo Co., Ltd.
Using M-IOE, room temperature 23 ° C and humidity 50% RH
Measure under the conditions of. (4) Scratch resistance Steel wool # 0000 on the sample surface
The sample was rubbed 10 times back and forth with and scratch resistance was indicated by O, Δ and x. (∘: good, Δ: acceptable, x: bad) (5) Adhesiveness It is evaluated by a cross stitch test (1 mm × 1 mm) by a cellophane tape peeling method.

Example 2 To 100 parts by weight of the lactone-modified polyvinyl alcohol obtained in Production Example 2, 300 parts by weight of ethylene oxide-added trimethylolpropane triacrylate as an acrylic monomer (B) and ethyl as an organic solvent were added. 100 parts by weight of alcohol and low molecular weight antistatic agent (made by Miyoshi resin, Dasper LA2000)
0.5 part by weight was stirred and mixed so as to be uniform at room temperature to obtain an antistatic coating composition. Using this product, the same operation as in Example 1 was performed to form a cured coating layer (thickness: 80 μm). The same test evaluation as in Example 1 was performed on this sample. The results are shown in Table 1.

Example 3 The lactone-modified polyvinyl alcohol used in Example 1 was changed to the methacryl group-added lactone-modified polyvinyl alcohol obtained in Production Example 3 except that the thickness of the cured coating layer was 100 μm. The same operation and test evaluation as in Example 1 were performed. The results are shown in Table 1.

[0052]

[Table 1]

[Comparative Examples 1 to 3] For comparison, instead of the lactone-modified polyvinyl alcohol in Example 1, in Comparative Example 1, polycaprolactone (manufactured by Daicel Chemical Industries, Ltd., PCL HIP, Mn = 10000) was compared. Example 2
Polyethylene glycol (NOF Corporation, # 1
100, Mn = 10000), and in Comparative Example 3, the same operation and test evaluation as in Example 1 were performed except that a polyvinyl alcohol (PVA403 manufactured by Kuraray Co., Ltd.) resin was used. Table 2 shows the results.

[Comparative Example 4] For comparison, the same operation as in Example 2 was performed except that the lactone-modified polyvinyl alcohol was not used in Example 2, and the same test evaluation as in Example 1 was performed. Table 2 shows the results.

[0055]

[Table 2]

Example 4 With respect to 100 parts by weight of the lactone-modified polyvinyl alcohol obtained in Production Example 1, 200 parts by weight of ethylene oxide-added trimethylolpropane triacrylate as a radical-polymerizable monomer (B), photoinitiated As an agent, 5 parts by weight of Darocur 1173 was stirred and mixed at room temperature to obtain an antistatic coating composition. This composition was applied to one side of a sheet (thickness: 2.0 mm) of a polycarbonate resin (Upilon S3000 manufactured by Mitsubishi Gas Chemical Co., Inc.) using the bar coat method. On this sheet, UV irradiation device (120w
/ Cm · 1 m) to cure the radically polymerizable monomer to form a coating layer (thickness: 50 μm) to obtain a colorless and transparent coated processed product. The same test evaluation as in Example 1 was performed on this sample. The results are shown in Table-3.
Shown in

Example 5 Example 4 was repeated except that the amount of the radically polymerizable monomer in Example 4 was changed to 400 parts by weight and the amount of the photoinitiator (Darocur 1173) was changed to 10 parts by weight. The same operation was performed to obtain a colorless and transparent coated product. The same test evaluation as in Example 1 was performed on this sample. The results are shown in Table-3.

[0058]

[Table 3]

[0059]

EFFECTS OF THE INVENTION According to the present invention, not only the antistatic agent does not fall off, but also the adhesion to the molded product, the toughness, the hardness, the scratch resistance, the chemical resistance and the water resistance are excellent. A molded product having an antistatic coating layer can be obtained.

Claims (5)

[Claims] 1. A lactone-modified polyvinyl alcohol (A) represented by the following general formula (1): 100 parts by weight, a radical polymerizable monomer (B): 10 to 1000 parts by weight, and an organic solvent (C): 0 to 1000 parts by weight. Coating composition consisting of parts. Embedded image 2. The antistatic coating composition according to claim 1, wherein the lactone-modified polyvinyl alcohol (A) represented by the general formula (1) has a radical-polymerizable group introduced therein. 3. An antistatic finish obtained by applying or impregnating a molded product with the antistatic coating composition according to claim 1 and then irradiating the molded product with active energy rays. Molded body. 4. The antistatically processed molded article according to claim 4, wherein the molded article is an artificial leather sheet, a fiber, clothes, OA equipment / home electric appliances or automobile parts. 5. An antistatic treatment, which comprises irradiating the molded body with an active energy ray after coating or impregnating the molded body with the antistatic coating composition according to claim 1. Method for manufacturing molded body.