JPH07292285A - Coating material composition - Google Patents

Abstract

PURPOSE:To obtain a marring-resistant, antistatic transparent coating material for synthetic resin products, particularly an optical disc, by mixing an oligomer having an ethylenic double bond with a polymerization initiator and a specified titanium compound. CONSTITUTION:A component (A) comprising an oligomer or monomer having a polymerizable ethylenic double bond in the molecule is mixed with a polymerization initiator (B) and a titanium compound (C) of formula I, II or III [wherein R<1> and R<5> are each a 20C or lower alkyl, an alkenyl, an aryl, etc.; R<3> is a 20C or lower alkyleneacyl, etc.; and R<2> and R<4> are each a 20C or lower alkyl, etc., having a side chain, etc., or a group of formula IV (wherein R<7>, R<8> and R<9> are each a 20C or lower alkyl, etc.)]. Examples of the component A include an oligomer modified with, e.g. a urethane, epoxy or polyester (meth)acrylate and a (meth)acrylic ester used for viscosity adjustment. For the effect of surface protection of a base material, the component A should contain at least 30wt.% oligomer or monomer having at least three (meth)acryloyl groups in the molecule, and for an improvement in the antistatic effect, it should contain polyether units.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating agent composition capable of imparting an antistatic function together with curing of a resin, and particularly excellent in scratch resistance and dust adhesion prevention to the surface of a plastic molding such as an optical disk. The present invention also relates to a coating agent composition for forming a coating agent layer.

[0002]

2. Description of the Related Art Plastics are widely used in the fields of wood products and metal products because of their workability and ease of mass production. Especially, transparent plastics such as acrylic resin and polycarbonate resin are light and resistant to cracking. It is used in some of the application fields of glass.

However, plastic has a drawback in that it has a soft surface and is easily scratched, which impairs its aesthetic appearance. In order to remedy this drawback, surface modification has conventionally been studied, in which a scratch-resistant protective film using a silicone-based or active energy ray-curable resin is attached.

By applying such a surface treatment, a coating film having scratch resistance is formed on the plastic surface. However, the former method requires heat treatment, so that the application to plastic is limited and the coating method is difficult. There are problems such as long curing time for film formation.

On the other hand, the latter method can form a coating film in a short time without the need for heat treatment which adversely affects plastic, but the formed coating film is also plastic. There is a problem that it is charged with static electricity and dust is easily attached.

As is well known, in general, plastic has a large electric resistance and is easily charged by friction or the like, so that dust or dust may be sucked to impair its appearance, or precision equipment that is extremely reluctant to dust may be adversely affected. In particular, in the fields of electricity and electronics, it is a cause of malfunction of equipment such as destruction of semiconductor elements due to electrostatic charging.

Therefore, antistatic methods for various plastics have been proposed today, and the antistatic methods can be broadly classified into those utilizing electron conductivity and those utilizing ionic conductivity.

[0008]

The former includes, for example, a method of kneading conductive particles such as carbon, metal and metal oxide into plastic, and a method of applying a conductive coating material containing them. This method has limited applications because most of the conductive particles are colored, and since it is necessary for the conductive particles to contact each other in order to release electricity, the amount of conductive particles added increases and the cost increases. There is a problem that leads to.

As the latter example, a method of adding or applying a surfactant or the like can be mentioned. In this method, although an excellent effect is exhibited in the initial stage, the effect is washed out by washing with water and the effect is exerted. However, there are problems such as disappearance and poor compatibility with organic materials.

Further, acrylic resin, polycarbonate resin, etc. are used for covers, nameplates, automobile parts, optical disk substrates, etc. of AV equipment and OA equipment by utilizing their excellent transparency, appearance characteristics and workability. However, particularly in such applications, properties having both scratch resistance and antistatic property are required.

Therefore, an object of the present invention is to provide a coating agent composition having good transparency, excellent scratch resistance, and excellent water resistance and an antistatic function.

[0012]

In order to solve the above problems, in the present invention, (a) an oligomer and / or a monomer having at least one polymerizable ethylenic double bond in the molecule, (b) ) Polymerization initiator and (c) at least one or more titanium compounds represented by the following general formulas (1), (2) and (3)

Embedded image [wherein R ¹ , R ⁵ and an alkyl group, an alkenyl group, an alkyloyl group, an alkenoyl group, an aryl group, an aralkyl group, R having a side chain or a substituent having up to 20 carbon atoms]
³ represents an alkylene group, an alkyleneacyl group, or an arylacyl group having a side chain or a substituent having up to 20 carbon atoms, and R ² and R ⁴ each represent an alkyl group having a side chain or a substituent having up to 20 carbon atoms, Alkenyl group, alkyloyl group, alkenoyl group, aryl group, aralkyl group, and

(In the formula, R ⁷ , R ⁸ and R ⁹ are each a carbon number of 20.
To the alkyl group, alkenyl group, alkyloxy group, aryl group, and aralkyl group each having a side chain or a substituent.

The (a) oligomer and / or monomer having at least one polymerizable ethylenic double bond in the molecule used in the present invention is a compound which is conventionally known as a component of a polymerizable resin composition. Can be used.

Specific examples of the oligomer include acrylate-based oligomers such as urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate, and oligomers modified with vinyl groups.

Further, for these, viscosity adjustment, curability,
The monomer component used for adjusting the adhesiveness and the like is also a compound having one or more polymerizable ethylenic double bonds in the molecule, and (meth) acrylic acid ester, (meth)
Acrylamides, styrene, N-vinylpyrrolidone,
Examples thereof include vinyl monomers such as N-vinylsuccinimide, but are not particularly limited thereto. Further, these oligomers and monomers are selected according to the purpose and application, and it is possible to use them alone or in combination of two or more kinds.

Here, in order to exert the scratch resistance of the cured film and the effect of protecting the surface of the substrate, the component (a) should have three or more reactive groups in the molecule of the oligomer and / or monomer. Is required, and the ratio is (a) component 100
It is necessary to include 30 parts by weight or more in the parts by weight.

As the reactive group, (meth) acrylate, which is rapidly polymerized by light, is preferably used. As such a polyfunctional oligomer, one obtained by introducing three or more reactive groups into the above-mentioned oligomer, and specific examples of the multi-possible monomer include trimethylolpropane tri (meth) acrylate and ditrimethylolpropane tetra (meth).
Acrylate, glycerol tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylech And so on.

The polymerization initiator is not limited as long as it has the ability to induce the polymerization reaction of the double bond in the resin composition to be used, and the addition amount may be a commonly used amount.

Specific examples of the polymerization initiator include inorganic peroxides, organic peroxides, combinations of peroxides with reducing agents, azo compounds, and photopolymerization initiators. Among these, polymerization by photocuring using a photopolymerization initiator capable of causing a polymerization reaction in a unit of seconds at room temperature is a plastic whose productivity and application of the coating agent of the present invention may be deformed by heat. It is preferably used from the viewpoints of being present.

These photopolymerization initiators can be used without particular limitation as long as they are usually conceivable, for example, benzophenone, benzoin, benzoin ethyl ether, benzoin methyl ether, benzoin isobutyl ether,
Benzoin propyl ether, benzyl dimethyl ketal, 1- (4-dodecylphenyl) -2-hydroxy-
2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-
1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2-hydroxyethoxy)
-Phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, methylphenylglyoxylate, 2-methyl-1- [4
-(Methylthio) phenyl-2-morpholinopropane]
Examples thereof include -1-one, chlorothioxanthone, diethylthioxanthone, isopropylthioxanthone, and diethoxyacetophenone. These can be used alone or in combination of two or more kinds.

The coating agent composition of the present invention comprises these curable resin compositions containing at least one of the titanium compounds represented by the following general formulas (1), (2) and (3). is there.

[0022]

[Chemical 1]

[Wherein R ¹ , R ⁵ and an alkyl group, an alkenyl group, an alkyloyl group, an alkenoyl group, an aryl group, an aralkyl group having a side chain or a substituent having up to 20 carbon atoms, and R ³ having up to 20 carbon atoms] An alkylene group having a side chain or a substituent, an alkyleneacyl group, an arylacyl group, and R ² and R ⁴ are each an alkyl group, an alkenyl group, an alkyloyl group, or an alkenoyl group having a side chain or a substituent having up to 20 carbon atoms. , An aryl group, an aralkyl group, and

[0024]

[Chemical 2]

(In the formula, R ⁷ , R ⁸ and R ⁹ each represent an alkyl group, an alkenyl group, an alkyloyl group, an aryl group, an aralkyl group, etc., having a side chain and a substituent having up to 20 carbon atoms). Show group]

Examples of the titanium compounds represented by the general formulas (1), (2) and (3) include isopropyl triisostearoyl titanate, isopropyl tri (dodecylbenzenesulfonyl) titanate, isopropyl trioctanoyl titanate and isopropyl dititanate. (Meth) acrylisostearoyl titanate, isopropyl tri (cumylphenyl) titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri [(N-aminoethyl) aminoethyl] titanate, bis (dioctyl pyro) Phosphate) oxyacetate titanate, dicumylphenyloxyacetate titanate, bis (dioctylpyrophosphate) ethylene thiate Sulfonates, diisostearoyl ethylene titanate, tetraisopropyl titanate,
Examples thereof include bis (dioctyl phosphite), tetraoctyl titanate bis (ditridecyl phosphite), and tetra (2,2-diallyloxymethyl-1-butyl) titanate bis (ditridecyl phosphite).

The amount of such a titanium compound to be added depends on the desired antistatic property, but is generally in the range of 0.1 to 10 parts by weight per 100 parts by weight of the component (a).

Further, by introducing a polyether structure into the cured product of the curable resin composition of the present invention, the antistatic ability can be improved. That is, it can be achieved by using the component (a) containing a polyether unit in the skeleton or by adding the component (d) polyether.

Specific examples of the component (a) containing such a polyether unit include urethane (meth) acrylates using polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc. ) Oligomer such as acrylic acid adduct, ethylene oxide modified trimethylolpropane tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, propylene oxide modified trimethylolpropane Tri (meth) acrylate, propylene oxide-modified pentaerythritol Tri (meth) acrylate, propylene oxide-modified pentaerythritol Tetra (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate etc. are mentioned.

As the polyether component, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and polyethers such as random copolymers and block copolymers thereof and condensation products of these with bisphenol and glycerin. Examples thereof include a polyol, an etherified product of a polyether polyol, and an esterified product of a polyether polyol.

The outline of the present invention has been described above. The curable resin composition of the present invention contains hydroquinone, hydroquinone monomethyl ether, benzoquinone, 2,6-ditert-butyl-p-cresol for improving storage stability. There is no limitation to add a polymerization inhibitor such as catechol or the like, or a known additive such as a defoaming agent, a colorant, an adhesion promoter, a leveling agent, etc. within a range that does not affect the properties of the cured product.

When the coating agent thus prepared is applied to a plastic molded body such as an optical disk substrate and polymerized and cured, a method of curing by irradiating with ultraviolet rays from the viewpoint of productivity and workability as described above Is suitable for
This makes it possible to form a transparent film which is excellent in scratch resistance and dust adhesion resistance, and whose antistatic effect does not easily disappear even when the surface is wiped with a polar solvent such as water or alcohol.

[0033]

EXAMPLES The present invention will be specifically described based on the following examples. The parts in the examples are parts by weight. Examples 1 to 4 40 parts of dipentaerythritol hexaacrylate, 1,
30 parts of 6-hexanediol diacrylate and 30 parts of tetrahydrofurfuryl acrylate are mixed, 5 parts of 1-hydroxycyclohexyl phenyl ketone is further added as a photopolymerization initiator, and 0.5 part of isopropyl tri (dodecylbenzenesulfonyl) titanate is prepared. Example 1), 1 part (Example 2), 5 parts (Example 3) and 10 parts (Example 4) were added and mixed to prepare a coating composition of the present invention. The obtained coating agent composition was applied onto a polycarbonate optical disk substrate using a spin coater, and was irradiated with ultraviolet rays using a high pressure mercury lamp to cure the coating film.

With respect to the optical disk substrate having the cured film thus obtained, the initial curing characteristics (pencil hardness, scratch resistance, adhesion, surface resistance value, dust adhesion) and surface resistance value after washing with water were observed, It was measured and evaluated. The evaluation results are shown in Table 1 below.
Shown in.

Pencil hardness test: According to JIS K-5400, a coating film hardness was measured by applying a load of 1 kg.

Scratch resistance test: The surface of the coating film was bencotted.
A load of 1 kg was rubbed and scratched, and the degree of scratches was evaluated using the microscope in the following two stages. ○: No scratches are recognized. X: A scratch is recognized. Adhesion test: According to JIS K-5400, 100 squares of 1 mm square
To make it possible to make individual pieces, make a cut so that it penetrates the coating film and reaches the fabric surface of the test piece, completely adhere the cellophane tape on it, and then momentarily separate the cellophane tape, and the remaining number of grids Was indicated by the number of remaining crosses / 100.

Surface resistance value: Measured by HIRESTA manufactured by Mitsubishi Yuka.

Dust adhesion test: After rubbing the surface of a test piece having a cured film with a cotton cloth 10 times, the test piece was brought closer to the ash of the cigarette, and the height at which the ash adhered was measured.

Example 5 A coating agent composition was prepared in the same manner as in Example 3 except that isopropyl tris (dioctyl pyrophosphate) titanate was used instead of isopropyl tri (dodecylbenzenesulfonyl) titanate. The obtained coating agent composition was applied and cured in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

Example 6 A coating agent composition was prepared in the same manner as in Example 3 except that bis (dioctylpyrophosphate) ethylene titanate was used instead of isopropyltri (dodecylbenzenesulfonyl) titanate. The obtained coating agent composition was applied, cured and evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 7 A coating composition was prepared in the same manner as in Example 3 except that tetraisopropyl titanate bis (dioctyl phosphite) was used instead of isopropyl tri (dodecylbenzenesulfonyl) titanate. The obtained coating agent composition was applied and cured in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

Comparative Example 1 A coating agent composition was prepared in the same manner as in Example 1 except that isopropyl tri (dodecylbenzenesulfonyl) titanate was omitted from the coating agent composition of Example 1. The obtained coating agent composition was applied and cured in the same manner as in Example 1 and evaluated. The results are shown in Table 1. The initial surface resistance value was 10 ¹³ Ω or more, and dust adhered.

Comparative Example 2 25 parts of dipentaerythritol hexaacrylate, 15 parts of tricyclodecane dimethanol diacrylate, 1,6
-Hexanediol diacrylate 30 parts and tetrahydrofurfuryl acrylate 30 parts were mixed, and 1-hydroxycyclohexyl phenyl ketone was further used as a photopolymerization initiator.
5 parts were added and mixed to prepare a coating composition.
The obtained coating agent composition was applied and cured in the same manner as in Example 1 and evaluated. The results are shown in Table 1 below.

[0044]

[Table 1]

Example 8 40 parts of dipentaerythritol hexaacrylate, 1,
20 parts of 6-hexanediol diacrylate, 20 parts of tetrahydrofurfuryl acrylate and 20 parts of polyethylene glycol diacrylate are mixed, and further 5 parts of 1-hydroxycyclohexyl phenyl ketone is added as a photopolymerization initiator, and isopropyl tri (dodecylbenzenesulfonyl) is added. ) 3 parts of titanate were added and mixed to prepare the coating composition of the present invention. The obtained coating agent composition was applied and cured in the same manner as in Example 1 and evaluated.
The results are shown in Table 2 below.

Example 9 After coating and curing in the same manner as in Example 1 except that ethylene oxide modified trimethylolpropane triacrylate was used instead of polyethylene glycol diacrylate,
An evaluation was made. The results are shown in Evaluation 2 below.

Example 10 40 parts of pentaerythritol triacrylate, 20 parts of trimethylolpropane triacrylate, 15 parts of 1,6-hexanediol diacrylate, 15 parts of tetrahydrofurfuryl acrylate and 10 parts of polyethylene glycol were mixed and further photopolymerized. 5 parts of 1-hydroxycyclohexyl phenyl ketone was added as an initiator, and 3 parts of isopropyl tri (dodecylbenzenesulfonyl) titanate was added and mixed to prepare a coating agent composition of the present invention. The obtained coating agent composition was applied and cured in the same manner as in Example 1 and evaluated. The results are shown in Table 2 below.

Example 11 A coating agent composition of the present invention was prepared in the same manner as in Example 7 except that polytetramethylene ether glycol was used instead of polyethylene glycol. The obtained coating agent composition was applied and cured in the same manner as in Example 10, and then evaluated. The results are shown in Table 2 below.

[0049]

[Table 2]

[0050]

As described above, the coating agent according to the present invention has a desired antistatic function by adding the titanium compound represented by the above (1), (2) and (3), and is resistant to It can form a cured film with excellent scratch resistance and moisture resistance and is useful as a plastic molding, especially as a coating agent for optical disks.

Claims (6)

[Claims] 1. (a) an oligomer and / or monomer having at least one polymerizable ethylenic double bond in the molecule, (b) a polymerization initiator and (c) the following general formula (1),
At least one of the titanium compounds represented by (2) and (3): Wherein the alkyl group having a side chain or substituent to R ^1, R ⁵ and 20 carbon atoms, an alkenyl group, alkyloyl group, alkenoyl group, an aryl group, an aralkyl group, the side chain of R ³ up to 20 carbon atoms And an alkylene group having a substituent, an alkyleneacyl group, an arylacyl group, and R ² and R ⁴ are each an alkyl group, an alkenyl group, an alkyloyl group, an alkenoyl group having a side chain or a substituent having up to 20 carbon atoms,
Aryl group, aralkyl group, and (In the formula, R ⁷ , R ⁸ and R ⁹ each represent an alkyl group, an alkenyl group, an alkyloyl group, an aryl group or an aralkyl group having a side chain or a substituent having up to 20 carbon atoms). A coating agent composition comprising: 2. A patent characterized by containing 30 parts by weight or more of one or more oligomers and / or monomers containing three or more (meth) acryloyl groups in the molecule in 100 parts by weight of component (a). The coating composition according to claim 1. 3. The coating according to claim 1 or 2, wherein the oligomer and / or monomer according to the component (a) contains a polyether unit in the main chain and / or side chain. Agent composition. 4. A coating agent composition comprising (a), (b) and (c) containing (d) a polyether component, as claimed in claims 1, 2 and 3. The coating composition according to the item. 5. The coating composition according to claim 2, 3 or 4, wherein a coating layer is formed by polymerizing and curing the surface of the plastic molded body. 6. The coating composition according to claim 5, wherein the molded product is an optical disk.