JP2000282014A - Antistatic hard coat resin composition and antistatic optical article and antistatic resin article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic hard coat resin composition which can limit the bleeding of an antistatic agent to a surface, the decrease of transparency, the deterioration of moisture resistance and the like within practically acceptable ranges, respectively, and has excellent scratch resistance and the like, by formulating a mixture of specific (meth)acryl-functional silane hydrolysates and the like. SOLUTION: This antistatic hard coat resin composition comprises (A) a mixture of the hydrolysate of a (meth)acryl-functional silane of formula I [R1 is H or methyl; R2 is a 3-6C divalent organic group; R3, R4 are each a (substituted) monovalent hydrocarbon; (a) is 0 to 2] (for example, 3- acryloxypropyltrimethoxysilane) with the hydrolysate of a quaternary ammonium salt structure-containing silane of formula II [R5 is a 1-6C alkyl; R6 is a 1-18C alkyl; X is a halogen; (b) is 0 to 2] (for example, N-trimethoxysilylpropyl-N,N,N- trimethylammonium chloride), (B) a polyfunctional (meth)acrylate such as pentaerythritol triacrylate, and (C) a photopolymerization initiator such as benzoin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photo-curing type charging device which mainly forms a film having excellent antistatic properties, scratch resistance, adhesion, moisture resistance, etc. on a resin surface such as plastic by irradiating ultraviolet rays or the like. The present invention relates to an antistatic hard coating agent, an antistatic optical article having a film formed by using the hard coating agent, and an antistatic resin body.

[0002]

2. Description of the Related Art Resins represented by synthetic resins not only have excellent properties such as light weight and toughness as compared with glass products, but also have advantages such as being inexpensive and easy to process. It is used in a wide range of fields such as optical components, optical disks, organic flat glass, and signboards. However, these synthetic resins have the drawback that they are easily scratched and are easily charged, so that they are easily dusted.

[0003] In order to improve these drawbacks, various methods have been studied for forming a crosslinked cured film on the surface of a resin by applying a photocurable resin composition and curing it by irradiation with ultraviolet rays.

[0004] However, although the abrasion resistance is greatly improved by the above-mentioned method, there is a problem in that it is easily charged due to friction or the like, and dust and the like adhere to it, thereby deteriorating the appearance.

Therefore, various methods for adding an antistatic agent to a photocurable resin composition have been proposed in order to improve these disadvantages.

However, in the method of adding an antistatic agent to a photocurable resin composition, when various surfactants such as cations, anions, and nonionics are added as an antistatic agent, an alkali is used as an antistatic agent. Metal salts,
When adding salts such as alkaline earth metal salts and ammonium salts, it is necessary to increase the amount of addition in order to obtain sufficient antistatic properties.

In this case, there arises a problem that the antistatic agent bleeds on the surface of the cured film.

Further, the method of adding a conductive filler such as a metal has an excellent antistatic property, but has a disadvantage that transparency is impaired.

The method of blending a phosphoric acid (meth) acrylate (Japanese Patent Publication No. 60-51511) has good initial antistatic properties and adhesion, but has problems such as insufficient moisture resistance. .

[0010]

SUMMARY OF THE INVENTION The present invention practically tolerates the above-mentioned side effects caused by the compounding of an antistatic agent, that is, bleeding of the antistatic agent onto the surface, deterioration of transparency, deterioration of moisture resistance, and the like. It is an object of the present invention to provide an antistatic hard coat resin composition which can be contained within a possible range and which satisfies functions as a hard coat (scratch resistance, surface hardness, moisture resistance, solvent / chemical resistance, etc.). .

[0011]

According to the present invention, (A) a hydrolyzate of an acrylic or methacryl functional silane represented by the formula (3) and a quaternary compound represented by the formula (4) are provided. The present invention has been found to be achieved by a resin composition obtained by blending a mixture of an ammonium salt structure-containing silane with a hydrolyzate, (B) a polyfunctional acrylate or methacrylate, and (C) a photopolymerization initiator. It is a thing.

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Further, there are provided an antistatic optical article on which a cured film of the hard coat resin composition is formed, and an antistatic resin body.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

As the acrylic or methacryl functional silane of the formula (A) used in the present invention, specifically, for example, 3-acryloxypropyltrimethoxysilane,
3-methacryloxypropyltrimethoxysilane, 3-
Acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane and the like are exemplified.

Next, the silane having a quaternary ammonium salt structure represented by Chemical Formula 4 is a component that contributes to antistatic properties.

More specifically, octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride,
Tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, N-trimethoxysilylpropyl-N, N, N-tri-n-butylammonium chloride, N-trimethoxysilylpropyl-N,
N, N-trimethylammonium chloride, N-trimethoxysilylpropyl-N, N, N-tri-n-butylammonium bromide and the like can be used.

The hydrolysis of Compounds 3 and 4 is carried out by adding and mixing pure water, or adding hydrochloric acid, nitric acid, sulfuric acid, acetic acid,
Acidic water added with an acid such as oxalic acid, citric acid, tartaric acid or the like as a catalyst or basic water added with a base such as ammonia, sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine or triethanolamine as a catalyst What is necessary is just to add and stir.

The degree of progress of hydrolysis can be controlled by controlling the amount of water added. Generally, the amount of water added is at least equimolar to the hydrolyzable group of the compound to be hydrolyzed. Desirably. In the hydrolysis of the compound, a solvent such as alcohols can be added for the purpose of homogenizing the hydrolysis reaction system.

Hydrolysis mixture of compound 3 and compound 4 (A)
May be prepared by separately hydrolyzing Compound 3 and Compound 4 according to the above method and then mixing them, or mixing Compound 3 and Compound 4 in advance and performing hydrolysis simultaneously. The compounding ratio of compound 3 and compound 4 is preferably about equimolar, but 1: 1.5 to 1.5: 1.
Molar ratios are within the scope of the present invention.

The mechanism of action of the component (A) is as follows. A hydrolyzate of an acrylic or methacryl-functional silane and a hydrolyzate of a silane having a quaternary ammonium salt structure form a film, and silanol groups condense during the drying process. In the ultraviolet irradiation treatment in the process, a copolymerization reaction with the component (B) described in detail below suppresses bleeding to the surface of the coating because it is incorporated into a crosslinked structure of the coating, thereby contributing to long-term stabilization of antistatic ability. It is considered something.

The polyfunctional acrylate or methacrylate as the component (B) used in the present invention is preferably a compound having three or more (meth) acryloyl groups in order to satisfy the surface hardness and abrasion resistance as a hard coat.

For example, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone Modified tris [(meth) acryloxyethyl] isocyanurate, pentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate and the like can be mentioned.

Examples of the compound having four (meth) acryloyl groups include trimethylolpropanetetra (meth) acrylate, pentaerythritoltetra (meth) acrylate, and alkyl-modified dipentaerythritoltetra (meth) acrylate. .

Examples of the compound having five (meth) acryloyl groups include dipentaerythritol penta (meth) acrylate and alkyl-modified dipentaerythritol penta (meth) acrylate.
Further, examples of the compound having six (meth) acryloyl groups include dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Also, a mixture of two or more of these compounds can be used. Among these compounds, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a mixture containing these are particularly preferred from the viewpoint of scratch resistance.

Further, as a reactive diluent for adjusting the viscosity of these resins, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate having relatively low viscosity are used. ) Bifunctional or more functional such as acrylate, hexanediol (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate Monomers and oligomers and monofunctional monomers, for example, acrylates such as N-vinylpyrrolidone, ethyl acrylate, propyl acrylate, ethyl methacrylate, propyl methacrylate,
Isopropyl methacrylate, butyl methacrylate,
Derivatives such as methacrylates such as hexyl methacrylate, isooctyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, nonylphenyl methacrylate, tetrahydrofurfuryl methacrylate, and modified caprolactone thereof, styrene, α-methylstyrene, acrylic acid, etc. And mixtures thereof.

As the photopolymerization initiator of the component (C) used in the present invention, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl methyl ketal and the like and alkyl ethers of radical-generating type; Acetophenones such as acetophenone, 2,2, -dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexylphenyl ketone; anthraquinones such as methylanthraquinone, 2-ethylanthraquinone and 2-amylanthraquinone; thioxanthones and 2,4-diethyl Thioxanthones such as thioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal;
Benzophenones such as benzophenone, 4,4-bismethylaminobenzophenone, and azo compounds.

These can be used alone or as a mixture of two or more kinds. Further, tertiary amines such as triethanolamine and methyldiethanolamine; benzoic acids such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate are used. It can be used in combination with a photoinitiating auxiliary such as a derivative. The amount of the photopolymerization initiator used is 0.5 to 20 parts by weight based on 100 parts by weight of the polymerizable resin component.
Parts by weight, preferably 1 to 15 parts by weight.

The hard coat layer of the present invention may optionally contain inorganic or organic fine particles, if necessary. Inorganic fine particles generally include fine particles made of silica, alumina, titania, zirconia, etc., but silica particles, particularly synthetic silica particles, are preferable in terms of transparency. In addition, conductive transparent fine particles such as tin oxide, indium oxide, cadmium oxide, and antimony oxide can also be used as necessary, regardless of imparting antistatic properties.

Further, the organic fine particles have an appropriate cross-linking structure inside the particles, and are made of an ultraviolet ray curable resin, a monomer,
Hard fine particles that are less swelled by a solvent or the like can be used.

For example, styrene resin, styrene-acrylic copolymer resin, acrylic resin, divinylbenzene resin, silicone resin, urethane resin, melamine resin, styrene-isoprene resin of particle internal cross-linking type,
Benzoguanamine resins, microgels containing the above resins and the like as main components, and the like can be used.

If necessary, well-known general paint additives can be blended within a range not affecting the antistatic performance. For example, silicone-based and fluorine-based additives for imparting leveling and surface slip properties are effective in preventing scratches on the cured film surface. By bleeding at the interface, the inhibition of curing of the resin by oxygen can be reduced, and an effective curing degree can be obtained even under low irradiation intensity conditions.

The appropriate amount of these additives is 0.01 to 0.5 parts by weight based on 100 parts by weight of the active energy ray-curable resin.

In order to cure the hard coat resin composition of the present invention with ultraviolet rays, a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc or the like can be used. A high-pressure mercury lamp is generally used for curing the film, and a metal halide lamp is generally used for the case where a filler is contained or the thick film is cured.

It is also possible to use an electron beam with a composition excluding the photopolymerization initiator, and specifically, a Cockloft-Wald type, a Bande-Craft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamic type It is preferable to use electron beams having an energy of 50 to 1000 KeV, preferably 20 to 300 KeV, emitted from various electron beam accelerators such as a tron type and a high frequency type.

An optical article is one whose performance cannot be exhibited or its performance deteriorates due to dust or dirt attached to the surface. It refers to spectacles, lenses typified by cameras, various recording media such as CDs and LDs that impair reading, architectural members such as wind films, display elements such as LCDs and projection screens, signboards, and automobile parts.

[0037] Further, the resin body is one in which disadvantageous phenomena such as quality deterioration occur due to dust and dirt adhering to the surface. Packaging materials such as films, bottles, bags, etc., such as food packaging materials and hygiene product packaging materials, which require a lot of hygiene considerations due to dust and dirt, and ICs and semiconductors that require attention to prevent static electricity generation Package and its packaging material.

[0038]

Next, the present invention will be described in detail with reference to examples. <Example 1> The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Parts and percentages are by weight unless otherwise specified.

100 g of 3-acryloxypropyltrimethoxysilane and N-trimethoxysilylpropyl-
N, N, N-trimethylammonium chloride 100
37 g of isopropyl alcohol for each g
After adding and stirring, 29 g of 0.05N diluted hydrochloric acid was added at about 10 ° C.
, And aged at room temperature for 6 hours to give 3-acryloxypropyltrimethoxysilane and N-trimethoxysilylpropyl-N, N, N-
Hydrolysates of trimethylammonium chloride were prepared separately.

Next, 8.3 g of a hydrolysis solution of 3-acryloxypropyltrimethoxysilane and 9.1 g of a hydrolysis solution of N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride were mixed, and the mixture was added thereto. After adding 30 g of methanol and aging at room temperature for 4 hours, 70 g of pentaerythritol triacrylate, 20 g of trimethylolpropane triacrylate, a photopolymerization initiator (D
arocure 1173, Nippon Ciba Geigy) 5
g was mixed to produce an ultraviolet-curable hard coat resin composition.

Next, the above-mentioned ultraviolet-curable hard coat resin composition was coated on one side of a 150 μm-thick double-sided easily-adhesive treated polyester film by wire bar coating.
After forming to a dry film thickness of about 5 μm, the coating film is irradiated with ultraviolet rays from a high-pressure mercury UV lamp (120 W / cm) under the condition of an integrated light quantity of about 400 mJ / m ² , and cured to cure, thereby charging. An anti-hard coat film was prepared.
The obtained hard coat film was evaluated by the following method.

Pencil hardness: 1K using pencils of different hardness
Under a load of g, the presence or absence of scratches was determined by a test method shown in JIS K5400.

Scratch resistance: The surface of the hard coat film was rubbed 10 times with a steel wool of # 0000 while applying a load of 400 g, and the presence or absence of scratches and the degree of scratches were visually observed. Was evaluated according to A: No scratch is observed. B: Several fine scratches are observed. C: Countless scratches are observed.

Surface resistivity (Ω / sq.): ASTM D
According to the requirements of 257, the measurement was performed by using a circular probe to avoid the influence of the electrode end.

High-temperature and high-humidity storage test: 60 ° C., 95%, 96
time

The obtained hard coat film had a pencil hardness of 3H and abrasion resistance of A, and had good mechanical performance as a hard coat. Initial surface resistivity is 7 × 10 ¹⁰
, Which showed practically satisfactory performance. Even after the high-temperature and high-humidity storage test, the surface resistivity was 9 × 10 ¹⁰ , and good performance was maintained without deterioration in appearance (decrease in transparency, surface bleeding, etc.) and no decrease in mechanical performance. .

Example 2 100 g of 3-acryloxypropyltrimethoxysilane and 110 g of N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride were mixed, and 78 g of isopropyl alcohol was mixed.
After adding and stirring, 61 g of 0.05N diluted hydrochloric acid was added at about 10 ° C.
, And aged at room temperature for 6 hours to give 3-acryloxypropyltrimethoxysilane and N-trimethoxysilylpropyl-N, N, N-.
A hydrolyzate of a mixed solution of trimethylammonium chloride was produced.

Next, 3-acryloxypropyltrimethoxysilane and N-trimethoxysilylpropyl-N, N,
30 g of methanol was added to 17.4 g of the hydrolysis solution of the N-trimethylammonium chloride mixed solution, and
After aged for 70 hours, 70 g of pentaerythritol triacrylate, 20 g of trimethylolpropane triacrylate, a photopolymerization initiator (Darocure 1173,
By mixing 5 g of Nippon Ciba Geigy Co., Ltd.), an ultraviolet-curable hard coat resin composition was produced.

The performance as an antistatic hard coat was examined by the same method for forming a hard coat, curing and evaluation as described in Example 1. As a result, as in Example 1, the pencil hardness was 3H, the scratch resistance was A, and the initial surface resistivity was 6 × 10 ¹⁰ , which is a sufficiently satisfactory performance for practical use. Even after the high-temperature and high-humidity storage test, the surface resistivity was 7 × 10 ¹⁰ , and good performance was maintained without causing deterioration in appearance and deterioration in mechanical performance.

<Comparative Example 1> As shown in the following formulation,
A composition obtained by simply mixing acryloxypropyltrimethoxysilane and N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride with a polyfunctional acrylate oligomer without performing a hydrolysis treatment was used as a hard coat coating liquid.

Prescription: 5 g of 3-acryloxypropyltrimethoxysilane, 5.5 g of N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, and 7 g of pentaerythritol triacrylate
0 g, 20 parts of trimethylolpropane triacrylate
g, 5 g of a photopolymerization initiator (Darocure 1173, manufactured by Nippon Ciba Geigy) and 37 g of methanol.

The same hard coat coating as described in Example 1.
When the performance was evaluated by the forming and curing methods, the pencil hardness was
Is 2H, the scratch resistance is A, and the initial surface resistivity is 2 ×
10 ^TenAlthough it showed satisfactory performance, high temperature and high humidity storage test
Later surface resistivity is 8 × 10¹²Rise to pencil hardness and ring resistance
The environment was unsatisfactory.

<Comparative Example 2> 17.5 g of the N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride hydrolyzed solution of Example 1 was mixed with an ultraviolet-curable resin composition having the following formulation, and coated with a hard coat. A liquid was produced.

Prescription: 70 g of pentaerythritol triacrylate, 20 g of trimethylolpropane triacrylate, and a photopolymerization initiator (Darocure 117)
3, 5 g of methanol manufactured by Ciba-Geigy, Japan)
g.

A hard coat film was formed in the same manner as in Example 1 and evaluated.

As a result, the initial surface resistivity was 3 × 10 ⁸
However, the pencil hardness was H to 2H, the scratch resistance was B, and the mechanical properties were significantly reduced. Also, after the high-temperature and high-humidity storage test, the surface of the coating film became slimy,
Surface bleeding of -trimethoxysilylpropyl-N, N, N-trimethylammonium chloride component was observed.

<Comparative Example 3> Except that 10.5 g of N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride was blended without using 3-acryloxypropyltrimethoxysilane of Comparative Example 1, The same hard coat resin composition as in Comparative Example 1 was used. A hard coat film was formed in the same manner as in Example 1 and evaluated.

As a result, the initial surface resistivity was 2 × 10 ⁸
However, when the UV curing treatment was completed, surface bleeding of the N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride component accompanied by a slimy feeling occurred on the surface of the coating film.

[0059]

As is apparent from the above description of the embodiments, a mixture of a hydrolyzate of acrylic or methacryl functional silane and a hydrolyzate of silane having a quaternary ammonium salt structure is used as an antistatic component. Thereby, the mechanical strength as the hard coat and the antistatic performance represented by the surface resistivity can be compatible at a practically satisfactory level.

The antistatic component of the present invention is fixed to the crosslinked structure of the coating by a copolymerization reaction with the hard coat resin component, and the silanol residue with time contributes to the densification of the crosslinked structure by dehydration condensation. No environmental bleeding and excellent environmental resistance can be maintained.

Accordingly, in the optical article having such an antistatic hard coat resin composition formed on the surface thereof, dirt and dust are less likely to adhere to the surface, and the optical performance of the optical article is less reduced. Also, since the resin body is less likely to adhere to the surface with dust and dirt, it is possible to maintain the beauty over a long period of time.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA13 AA19 AB14 AB20 AC01 AD01 BC13 BC40 BC42 BC50 BC78 BC83 BC87 BJ10 CA00 CB33 CC10 DA38

Claims (3)

[Claims] (A) A hydrolyzate of an acrylic or methacryl functional silane represented by the formula (1), and
A mixture of a quaternary ammonium salt structure-containing silane with a hydrolyzate, (B) a polyfunctional acrylate or methacrylate,
(C) An antistatic hard coat resin composition comprising a photopolymerization initiator. Embedded image Embedded image 2. An antistatic optical article having a cured film of the antistatic hard coat resin composition according to claim 1 formed on the surface. 3. An antistatic resin body having a cured film of the antistatic hard coat resin composition according to claim 1 formed on the surface.