JPH0480266A - Antistatic ultraviolet-curing coating material - Google Patents

Abstract

PURPOSE:To obtain the title material which can give a coating film excellent in scuff resistance, solvent resistance and antistatic properties by mixing a specified antistatic composition with a compound selected from among copolymerizable esters and a photopolymerization initiator. CONSTITUTION:An antistatic composition comprising a thiocyanate [e.g. Bs(SCN)2] and an alkylene glycol chain-containing anionic surfactant (e.g. sodium polyoxyethylene laurylphenyl ether sulfate) is mixed with at least one compound selected from among copolymerizable (meth)acrylic esters (e.g. dipentaerithritol hexaacrylate, polyethylene glycol diacrylate and 2-hydroxyethyl acrylate) and a photopolymerization initiator (e.g. methyl phenylglyoxylate).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an antistatic coating material for synthetic polymer molding materials, particularly an ultraviolet curable antistatic coating material.

(Prior Art) Synthetic polymer molding materials are usually highly hydrophobic and, as a result, have the property of being easily charged, and these properties can cause problems such as dust attraction, electric shock, ignition, etc. when using products using these materials. This is an obstacle to the above.

Conventionally, in order to prevent charging of polymeric materials, conductive agents such as carbon or conductive metal bundles, or surfactants, etc., have been used.
Attempts have been made to prevent various troubles by kneading them into polymeric materials or applying them to their surfaces. For example, Japanese Patent Application Laid-Open No. 63-307947 discloses a method of coating a charge transfer complex on a film. However, in order to obtain desired charging characteristics using a conductive agent such as a charge transfer complex, a large amount of the conductive agent is required.

In addition, it is not common because the method of adding the charge transfer complex is difficult, it is difficult to obtain a transparent one, and the conductive agent is expensive, and the range in which it can actually be used is quite limited.

On the other hand, antistatic agents mainly composed of surfactants are appropriately selected from among many types and are used in large numbers. Among these, there are many proposals for internal addition types that are kneaded into polymeric materials (Japanese Patent Laid-Open Publication No. 63-314261, etc.). On the other hand, in coating type antistatic agents applied to the surface of polymeric materials, surfactants are used alone or together with polymers and other substances, but these conventional antistatic agents are not sufficiently effective, for example, in low humidity conditions. There are many products that have insufficient durability, or their effectiveness disappears due to heating, friction, washing, etc. during the drying process, stretching, heat setting, heat molding, etc. after application. Something was desired.

In addition, UV-curable coating materials not only have a wide selection of base materials and short processing times, but also have excellent coating film performance such as chemical resistance, scratch resistance, and abrasion resistance. There was a problem in that static electricity was generated due to such factors, and dust was likely to adhere. As a solution to this problem, as disclosed in JP-A No. 61-6064, a proposal has been made to utilize the compatibility balance by adding a phosphoric acid ester to promote surface orientation of the antistatic agent. However, it has been difficult to form a coating film with a good balance of mechanical strength, durability, and sustainability of antistatic performance in long-term tests such as moisture resistance tests.

[Problem to be solved by the invention]

Under such circumstances, the object of the present invention is to provide an antistatic composition comprising a combination of a thiocyanate and an anionic surfactant having an alkylene glycol chain as a component constituting the coating film for coating a polymer molding material. It is an object of the present invention to provide a coating material that, when used, ensures the excellent scratch resistance and solvent resistance that conventional ultraviolet curable coating materials have, and can form a coating film having antistatic properties.

[Means and effects for solving the problem] The above object is to contain an antistatic composition comprising a combination of a thiocyanate and an anionic surfactant having an alkylene glycol chain as a coating material component of the present invention. This is achieved by providing an antistatic ultraviolet curable coating material characterized by:

To explain in more detail, the antistatic UV-curable coating material according to the present invention comprises an antistatic composition comprising a combination of a thiocyanate and an anionic surfactant having an alkylene glycol chain, and a copolymerizable (meth) )
It is characterized by containing at least one compound selected from acrylic esters and a photopolymerization initiator. Specific examples of the thiocyanate constituting the antistatic composition of the present invention include sodium thiocyanate, potassium thiocyanate, barium thiocyanate, ammonium thiocyanate, zinc thiocyanate, and the like. Among them, barium thiocyanate, potassium thiocyanate, and sodium thiocyanate are preferred from the viewpoint of solubility and cost.

Further, examples of anionic surfactants having an alkylene glycol chain include alkyl ether sulfates such as polyoxyethylene alkylphenyl ether, polyoxypropylene alkylphenyl ether, polyoxyethylene alkyl ether, and polyoxypropylene alkyl ether; Higher alcohol ethoxy sulfates such as alkyl ether phosphates, lauryl alcohol ethoxy, lauryl alcohol propoxy, oleyl alcohol ethoxy, oleyl alcohol propoxy, stearyl alcohol ethoxy, stearyl alcohol propoxy, higher alcohol propoxy sulfates, and their phosphoric acid esters, etc. Can be mentioned. Among these, polyoxyethylene alkylphenyl ether sulfate is preferred from the viewpoint of solubility and compatibility.

The ratio of the combination of these thiocyanate and anionic surfactant is preferably in the range of 60 to 99% by weight of thiocyanate and 1 to 40% by weight of anionic surfactant. If the amount of anionic surfactant used exceeds 40 parts by weight, it becomes difficult to obtain a special antistatic effect, and the surface hardness of the cured coating film tends to decrease.

Examples of copolymerizable (meth)acrylic esters to be mixed with this antistatic composition include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate. )
Acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate,
Adducts of ethylene oxide or propylene oxide to hydroxyl group-containing (meth)acrylic acid esters such as 4-hydroxypentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate2- Examples include dimers or trimers of hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

The amount of these hydroxyl group-containing (meth)acrylic esters used is in the range of 0 to 20% by weight, preferably 5% by weight.
-lO wt% range. When the amount used exceeds 20% by weight, the adhesion between the coating film and the substrate tends to decrease.

Examples of acrylic esters that are effective as crosslinking agents for scratch resistance of paint films and surface protection of substrates include various (meth)acrylate compounds as described below.
One or more of these may be selected and used. Specific examples of polyvalent acrylates include trimethylolpropane tri(meth)acrylate, trimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and glycerin tri(meth)acrylate.
meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)
Acrylate, dipentaerythritol penta(meth)
Acrylate, dipentaerythritol hexa(meth)
Examples include acrylate and its ethylene oxide or propylene oxide adduct, and specific examples containing two (meth)acryloyl groups in the molecule include:
■, 3-butanediol di(meth)acrylate, 1.
4-butanediol di(meth)acrylate, 1.6-
Hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, cyclopentadienyl alcohol di(meth)acrylate Examples include (meth)acrylate.

Examples of (meth)acrylate compounds other than the polyvalent esters mentioned above include reactions between polybasic acids such as phthalic acid and adipic acid, and polyhydric alcohols such as ethylene glycol, hexanediol, and butanediol, and (meth)acrylic acid. Polyester poly(meth)acrylate obtained by, epoxy(meth)acrylate obtained by esterifying the epoxy group of an epoxy compound with (meth)acrylic acid, (meth)acrylate having a hydroxyl group in hexamethylene diisocyanate, such as 2-hydroxyethyl acrylate. Reacted melamine (meth)acrylate, urethane poly(meth)acrylate obtained by reaction of polyol, polyisocyanate, and hydroxyl group-containing monomer such as 2-hydroxyethyl acrylate, reaction of polysiloxane and (meth)acrylic acid compound Polysiloxane obtained by poly(meth)acrylate, polyamide and (meth)
Examples include polyamide poly(meth)acrylate obtained by reaction with an acrylic acid compound.

The preferred amount of these polyfunctional (meth)acrylates used is 50 to 80 parts by weight. If the amount used is less than 50% by weight, the surface protection performance such as the scratch resistance of the coating film tends to deteriorate, and if it exceeds 80% by weight, the surface orientation of the antistatic composition is hindered, and the antistatic composition is not sufficiently There is a tendency that the antistatic performance cannot be exhibited.

Furthermore, as those having one (meth)acryloyl group in the molecule, 2-ethylhexyl (meth)acrylate, ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (
Examples include meth)acrylamide and the like.

The amount of these monofunctional (meth)acrylates used is 0 to 1
5% by weight is preferred. If the amount used exceeds 15% by weight, the curing performance of the coating film tends to decrease. Further, among these (meth)acrylate compounds, those having an acryloyl group in the molecule are particularly preferably used in the present invention because they provide better results in curability than those having a methacryloyl group.

Examples of photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, which have absorption properties in the ultraviolet region of 260 to 450 nm. Jetoxyacetophenone, a,a-dimethoxy-a-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4゜4
Carbonyl compounds such as -bis(dimethylaminobenzophenone) and 2-hydroxy-2-methyl-1-phenylpropan-1-one, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, azobisisobutyro Nitrile, azobis-2,
Examples include azo compounds such as 4-dimethylvaleronitrile, and peroxides such as benzoyl peroxide and ditertiary-butyl peroxide.

The above photopolymerization initiator may be used alone or in a mixture of two or more, and the amount used is 100 parts by weight in total of the antistatic composition and acrylic ester as shown in the claims. In general, 0.2 to 10 parts by weight may be used.

The antistatic ultraviolet curable coating material according to the present invention may contain the following conventionally known components in order to satisfy its quality performance. That is, additives such as surface conditioners, ultraviolet absorbers, and antioxidants may be included as appropriate.

There are no particular limitations on the coating method and curing method for the antistatic ultraviolet curable coating material obtained by blending the above-mentioned components using a general blending method. As a source of ultraviolet rays, a high pressure mercury lamp, a metal halide lamp, etc. can be used.

(Example) Next, the content of the present invention will be explained in more detail using typical examples. However, these are merely examples, and it is clear that the application examples of the present invention are not limited to these.

22g of dipentaerythritol hexaacrylate (hereinafter referred to as DPHA) as the second polyfunctional acrylate in history
1 6 g of polyethylene glycol diacrylate, 1 g of 2-hydroxyethyl acrylate (hereinafter referred to as HEA) as a monofunctional acrylate, barium thiocyanate according to the present invention (hereinafter referred to as Ba(SCN)z), and anion. As a surfactant, sodium lauryl phenyl ether sulfate (hereinafter referred to as CI+H*sP h O (E O) a
It's called S 03N a. ) at a mixing ratio of 10:1 was uniformly blended in the amounts shown in Table 1, and Ig of methylphenylglyoxylate (hereinafter referred to as MPG) was added as a photopolymerization initiator. This coating material was applied to a polycarbonate molded plate using a bar tool to a dry film thickness of 8.5 to 9.5 μ-, and a film was formed by irradiation with ultraviolet rays, and the antistatic performance of the film was tested. did. The results are shown in Table 6.

22 g of DPHA as a polyfunctional acrylate, 6 g of polyethylene glycol diacrylate, 1 g of HEA as a monofunctional acrylate, Ba(SCN)z and Cz
A 10:1 mixture of H2sPhO (EO) and SO3Na was uniformly blended in the amounts shown in Table 2, and M was added as a photopolymerization initiator.
Added 1 PG. This coating material was irradiated with ultraviolet rays in the same manner as in Example 1 to form a coating film, and the antistatic performance of the coating film was tested.

The results are shown in Table 6.

Table 18g of DPHA as a polyfunctional acrylate, 8g of HEA as a monofunctional acrylate, Ba(SCM)2 and CIIH23P h O(E 0)sS Os Na
were mixed in the ratio shown in Table 3, 1 g of this was uniformly blended, and 0.2 g of MPG was added as a photopolymerization initiator. This coating material was irradiated with ultraviolet rays in the same manner as in Example 1 to form a coating film, and the antistatic performance of the coating film was tested.

Table 3: 22 g of DPHA as a polyfunctional acrylate, 6 g of polyethylene glycol diacrylate, 1 g of HEA as a monofunctional acrylate, 10=1 of thiocyanate and anionic surfactant as shown in Table 4 according to the invention. 1 g of the mixture was homogenized, and 1 g of MPG was added thereto as a photopolymerization initiator. This coating material was irradiated with ultraviolet rays in the same manner as in Example 1 to form a coating film, and the antistatic performance of this coating film was tested.

The results are shown in Table 6.

Table 4: 18 g of DPHA as a polyfunctional acrylate, 8 g of HEA as a monofunctional acrylate, Ba(S CM)2
1 g was uniformly blended, and MPG was further added as a photopolymerization initiator.
0.2g of was added. This coating material was irradiated with ultraviolet rays in the same manner as in Example 1 to form a coating film, and the antistatic performance of the coating film was tested.

The results are shown in Table 6.

Kita Shibokumasu I 22 g of DPHA as a polyfunctional acrylate, 10 g of polyethylene glycol diacrylate, 1 g of HEA as a monofunctional acrylate, M as a photopolymerization initiator
1 g of PG was added. This coating material was irradiated with ultraviolet rays in the same manner as in Example 1 to form a coating film, and the antistatic performance of the coating film was tested.

The results are shown in Table 6.

18g of DPHA as a polyfunctional acrylate, 8g of HEA as a monofunctional acrylate, 1g of Ba(SCN)z and C++H+zPho(EO)ssOsNa were mixed in the proportions shown in Table 5, and 1g was uniformly mixed on a table. To this was added 0.2 g of MPG as a photopolymerization initiator. This coating material was irradiated with ultraviolet rays as in Example 1 to form a coating film, and the antistatic performance of the coating film was tested.

The results are shown in Table 6.

Table 5: 22 g of DPHA as a polyfunctional acrylate, 6 g of polyethylene glycol diacrylate, 1 g of HEA as a monofunctional acrylate, Cl1H23PhO (E
O) 5 g of sSOxNa and 1 g of MPG as a photopolymerization initiator were added. This coating material was irradiated with ultraviolet rays in the same manner as in Example 1 to form a coating film, and the antistatic performance of the coating film was tested.

The results are shown in Table 6.

(Effects of the Invention) The coating material according to the present invention has excellent scratch resistance and solvent resistance compared to conventional ultraviolet curable coating materials, and at the same time forms a coating film having antistatic properties.

January 14, 1991

Claims (1)

[Claims] An antistatic composition comprising an anionic surfactant having a thiocyanate and an alkylene glycol chain, at least one compound selected from copolymerizable (meth)acrylic esters, and a photopolymerization initiator. An antistatic ultraviolet curable coating material characterized by a mixture of.