JPH01161027A - Curable composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a specific composition that is cured by ultraviolet rays, electron beams, etc. and forms a coating film with excellent physical properties. More specifically, a cured coating film is formed on a transparent plastic substrate,
The present invention relates to a composition that imparts antistatic properties and abrasion resistance to a substrate without impairing the transparency of the substrate.

BACKGROUND OF THE INVENTION Plastic materials such as polycarbonate, polymethyl methacrylate, and polyvinyl chloride are lightweight and have excellent transparency, so they are used as replacements for various storage containers, covers, and window glasses.

However, these materials have low surface hardness and are easily scratched.
That is, it has a number of drawbacks such as low abrasion resistance and easy charging, which attracts dust, and a solution to these drawbacks has been determined.

Conventionally, as one method to solve the drawback of low surface hardness, a method of applying a composition that forms a transparent cured film to the surface of a plastic material has been considered. At that time, compositions that form a cured film by irradiation with ultraviolet rays or electron beams are often used, and typical compositions include acrylic or methacrylic oligomers.

On the other hand, as a method to solve the problem of dust adhesion caused by static electricity, the use of antistatic agents is being considered, and in particular,
A typical method is to add an antistatic agent to the oligomer.

Problems to be Solved by the Invention However, when such an antistatic agent is added in an amount sufficient to exhibit antistatic ability, it causes a significant decrease in the abrasion resistance of the coating film, which poses an obstacle to practical application. It became.

In order to put these coating films into practical use, it is essential to have a composition that can form a cured coating film that has both antistatic ability and abrasion resistance. That is, specifically, as antistatic ability,
Surface resistivity (Ω) (based on ASTM D-257) is 1.
If the haze value (%) after the taper test (according to ASTM D-1004, C3I0.500g x 2.100 rotations) is not less than 5 as wear resistance, it will be difficult to put the coating into practical use. It is.

There is no conventional product that satisfies these requirements at the same time, and only satisfies one of the requirements. For example, in Japanese Patent Publication No. 62-21815, a cured film is formed from a composition of an acrylic or methacrylic oligomer and a finely powdered inorganic filler whose surface is treated with a silicon compound. However, the physical properties such as abrasion resistance were merely improved, and the physical properties such as antistatic ability were not improved at all.

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors developed a method for surface treatment by hydrolyzing an acrylic or methacrylic compound and a specific organosilicon compound. When adding an antistatic agent to a composition consisting of a fine powdered inorganic filler, the problem of reduced wear resistance, which is a drawback of adding an ordinary antistatic agent, can be avoided.
The present invention was completed by discovering that it is possible to form a cured film that has both excellent antistatic ability and extremely high abrasion resistance.

That is, the present invention provides (A) a compound containing two or more acryloyl groups or methacryloyl groups in its molecule, (B) an antistatic agent, and (C) an inorganic compound whose surface has been treated by hydrolysis of an organosilicon compound represented by the following formula. Filler R' R2S i (OR') 4. (m, n)n [In the formula, RISR2 is a hydrocarbon residue having 1 to 20 carbon atoms or an organic group having a halogen, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or an amino group; , R1 is a hydrocarbon residue having 1 to 6 carbon atoms or an oxygen-containing hydrocarbon residue, m%n is 0.1 or 2, and (
m+n) is 1 or 2. ] The present invention relates to a curable composition containing these as essential components.

Hereinafter, the photocurable composition of the present invention will be explained in detail.

The compound having an acryloyl group or methacryloyl group referred to as component (A) of the present invention is usually a carbon atom compound having 8 to 30 carbon atoms, such as ethylene glycol diacrylate, propylene glycol diacrylate, Examples include trifunctional acrylates or methacrylates such as methacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol dimethacrylate. Additionally, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol triacrylate, glycerol trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, tris-(2-hydroxyethyl)-isocyanurate acrylate, tris-(2-hydroxyethyl)-isocyanurate acrylate, -Hydroxyethyl)-isocyanurate ester methacrylate and other trifunctional or higher functional acrylates or methacrylates.

In addition, it has a relatively large molecular weight (molecular weight approximately 300 to 10,
000) compounds such as polyester acrylates,
Epoxy acrylates, polyurethane acrylates, etc. are also used.

Note that a reactive monofunctional acrylate or methacrylate may be used in combination for the purpose of lowering the viscosity of the curable composition. Examples of these monofunctional compounds include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate.

As the antistatic agent referred to in component (B) of the present invention, ordinary surfactants can be used, including nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. For example, nonionic surfactants include N,N-bis(2-hydroxyethyl)alkylamine, polyoxyethylenealkylamine, fatty acid ester of polyoxyethylenealkylamine, glycerin fatty acid ester, sorbitan fatty acid ester, and polyoxyethylenealkylamine. Examples include oxyethylene sorbitan fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene alkylphenyl ether, and polyethylene glycol fatty acid ester. Examples of anionic surfactants include alkyl sulfonates, alkylbenzenesulfonates, alkyl sulfates, and alkyl phosphates, and examples of cationic surfactants include tetraalkyl ammonium salts and trialkylbenzyl meamimonium salts. Examples of amphoteric surfactants include alkyl betaines. Among these, polyoxyethylene alkylamine is particularly preferred.

The antistatic agent (B) can be used in an amount of 5 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of component (A). If the amount is less than 5 parts by weight, the cured coating film will not exhibit sufficient antistatic ability.

Moreover, if the amount is more than 50 parts by weight, wear resistance will decrease.

Component (C) of the present invention has the general formula % () 1 where R1% R2 is a hydrocarbon residue having 1 to 20 carbon atoms, a halogen, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or an amino group. It is an organic group having a 5i-C bond with silicon, where R is a hydrocarbon residue having 1 to 6 carbon atoms or an oxygen-containing hydrocarbon residue, and ms n is 0.1 or 2. and (m+n) is 1 or 2. ] This is an inorganic filler whose surface has been treated by hydrolysis of an organosilicon compound.

Specific examples of organosilicon compounds represented by the above general formula include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. ethoxysilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, trimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane , γ-chloropropyltriacetoxysilane, 3.3.3-trichloropropyltrimethoxysilane, γ-glycidoxyprobyltrimethoxysilane, γ-glycidoxybrobyltriethoxysilane, γ
-(β-glycidoxyethoxy)propyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, γ-methacryloxypropyltri Methoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercabutobrobyltriethoxysilane, N-β
Trialkoxy or triazyloxysilanes such as (aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyldimethoxysilane, phenylmethyldimethoxysilane,
Dimethyljethoxysilane, phenyl, methyljethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycid Xypropylphenyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ
-chloropropylmethyljethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyljethoxysilane, Examples include alkoxysilanes or diacyloxysilanes such as γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyljethoxysilane, methylvinyldimethoxysilane, and methylvinyljethoxysilane.

These silicon compounds can be used alone or in combination of two or more.

Among these compounds, R1 or R2 contains curable carbon.
Those having a carbon double bond are preferably used. That is, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, methylvinyldimethoxysilane, Methylvinyljethoxysilane and the like are preferably used.

Typical inorganic fillers include silica and alumina, but clay, talc, mica, asbestos, calcium silicate, glass powder, titania, magnesia, and the like may also be used. These inorganic fillers are preferably in the form of fine powder, that is, those with small particle sizes.
Particle size is 0.001 to 1 μm, preferably 0.007 to 0
．． 020 μm is preferably used. Specifically, AERO3I L-380, 300, 200 as silica
, 130 (manufactured by Degussa, West Germany) and Hi-8TL
(manufactured by PPG, USA), and examples of alumina include ALON (manufactured by Alcan, Canada).

Component (C) of the present invention can be obtained by treating the surface of these inorganic fillers with a hydrolyzate of an organosilicon compound represented by the above-mentioned general formula.

That is, hydrolysis of the organosilicon compound is performed by dispersing the organosilicon compound in water, and -S 1-
A hydrolysis product having an OH bond, a -8i-0-S i-0 bond, etc. is obtained. An inorganic filler is added to this hydrolyzate and dispersed by stirring. Then,
By evaporating and removing water, the surface of the inorganic filler is coated with the hydrolyzate. Note that by this treatment, a part of the hydrolyzate is chemically bonded to the surface of the inorganic filler. Component (C) is thus obtained. The amount of the organosilicon compound used is 5 to 50 parts by weight, preferably 10 to 40 parts by weight, per 100 parts by weight of the inorganic filler. If the amount used is less than 1 part of 5ff, the final coating film formed using the photocurable composition will have poor transparency and abrasion resistance, and
When the amount is more than 50 parts by weight, a portion of the hydrolyzate of the organosilicon compound remains without reacting with the inorganic filler, resulting in a decrease in the abrasion resistance of the coating film.

The component (C) of the present invention synthesized in this way is the component (
A) It can be used in an amount of 5 to 100 parts by weight, preferably 10 to 75 parts by weight, based on 100 parts by weight. If it is less than 5 parts by weight, the abrasion resistance of the coating film formed using the photocurable composition finally obtained will decrease, and if it is more than 100 parts by weight, the transparency of the coating film will be impaired.

In order to improve the photocurability of the curable composition of the present invention, a photosensitizer can be used in an amount of 0.1 to 10%. Examples of photosensitizers include ketals such as benzyl dimethyl ketal, benzyl dimethyl ether, benzoin ethyl ether, benzoin-1-propyl ether, benzoin,
Benzoins such as α-methylbenzoin, 9.10-
Anthraquinones such as anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, and 2-ethylanthraquinone; benzophenones such as benzophenone, p-chlorobenzophenone, and p-dimethylaminobenzophenone; 2-hydroxy-2-methylpropiophenone; Propiophenones such as -(4-isopropylphenone)-2-hydroxy-2-methylpropiophenone, suberones such as dibenzosuberone, ionic compounds such as diphenyl disulfide, tetramethylthiuram disulfide, thioxanthone, methylene blue, Examples include pigments such as eosin and fluorescein, and these photosensitizers may be used alone or in combination of two or more.

The curable composition in the present invention comprises the components (A) and (B).
) and (C). The mixing method is not particularly limited, but usually components (A), (B) and (C
) is mixed and kneaded with an appropriate organic solvent. As the device used for dispersion, for example, a three-roll mill, a sand mill, a ball mill, etc. can be used. Mixing conditions vary depending on the mixing device, but for example, when using three rolls, uniform dispersion can be achieved by mixing at 20 to 100° C. for 10 to 100 minutes.

The curable composition of the present invention thus prepared is applied to a plastic sheet or film by a conventional method such as a spray method, a dipping method, a roll coater method, or a spinner method. Examples of plastic sheet or film base materials include highly transparent polycarbonate, acrylic resin, polyethylene terephthalate,
Suitable materials include polyvinyl chloride. After coating in this way, the solvent is evaporated at room temperature or heated as appropriate.
It is cured by irradiation with light, electron beam, etc.

Curing conditions are not particularly limited, but usually vary depending on the type of energy source to be irradiated. For example, when using a high-pressure mercury lamp, curing conditions are
A preferred cured film is obtained by irradiating for 0.5 to 10 seconds at an energy density of 0 mW/cJ (366 mm).

Effects of the Invention According to the curable composition of the present invention, it is possible to form a coating film that is cured by light or electron beams and has excellent abrasion resistance and hardness, as well as excellent transparency and antistatic properties. Therefore, semiconductor wafer storage containers, television front panels, organic window glass,
It is used for applications such as lighting equipment covers where scratches, dust, and static build-up should be avoided.

EXAMPLES The present invention will be explained in detail with reference to Examples below, but the present invention is not limited thereto.

The physical properties of the cured film obtained from the curable composition of the present invention were determined according to the following method.

Haze value: ASTM D-1003 Taper test: CS based on ASTM D-1004
10,500gX2. 100 revolutions surface solid a resistance: ASTM D-257 Synthesis of surface treated inorganic filler (G-1) 200 g of γ-acryloxypropyltrimethoxysilane was soaked in water adjusted to pH -4.2 at 4°C for 1 hour. Disperse while stirring. Next, 800g of finely powdered silica (D
egussa AEROS I L-380) using a homogenizer with a high-speed stirrer (NIROATOMIZE).
A dispersion liquid was prepared by stirring for 20 minutes using a vacuum cleaner (manufactured by R. Co., Ltd., Denmark). This dispersion was heated in a spray dryer [manufactured by Tokushu Kakoki Kogyo Co., Ltd.] for about 1 hour to keep the air temperature at about 90°C.
/ hr and dehydrated and dried to obtain a surface-treated inorganic filler (G-1).

Synthesis of surface-treated inorganic filler (G-2) Surface-treated inorganic filler (G-2) was obtained in the same manner as (G-1) except that 100 g of vinyltrimethoxysilane and 900 g of finely powdered silica were used. Ta.

Example 1 A mixture containing 1/3 each of the kings of urethane acrylate oligomer (Eb-220 manufactured by UCB, Belgium), 1,6-hexanediol acrylate, and trimethylolpropane triacrylate by weight (hereinafter referred to as oligomer mixture A) was added to 100 g. On the other hand, non-ionic antistatic agent (
Add 20 g of Kao Electrostripper EA), 25 g of surface-treated inorganic filler (G-1,), and 6 g of photosensitizer (Ciba Geigy 1 RGACURE RE184),
50℃ using three rolls. A kneaded product was obtained under the conditions of 60 minutes.

100g of this mixture and solvent (ethyl acetate 30, η-Bu
100 g of OH70) were mixed and stirred to obtain a composition. This composition was applied onto a polycarbonate plate (Mitsubishi Gas Chemical) using a spinner, dried at 50°C for 10 minutes, and then heated at 120W.
1 from a distance of 10 countries using a high-pressure mercury lamp of /cln.
Irradiation was performed for 0 seconds to obtain a cured film with a thickness of 5 μm.

Table 1 shows the results of evaluating the physical properties of this cured film.

As is clear from Table 1, the obtained cured film has an extremely small hemisphere value of 0.1%, and a surface resistivity of 4.6%.
X1011 is small, and the haze value after the taper test is also 3.
It was as small as 7%, and was extremely excellent in all physical properties.

Example 2 Example 2 except that the surface-treated inorganic filler (G-1) in Example 1 was replaced with the surface-treated inorganic filler (G-2).
A cured film was obtained by performing the same operation as above.

The physical property evaluation results of the obtained cured film are shown in Table 1. Similarly to Example 1, Example 2 was also extremely excellent in all physical properties.

Comparative Example 1 The same procedure as Example 1 was carried out except that the nonionic antistatic agent and inorganic filler were not used.

Table 1 shows the results of physical property evaluation of the obtained cured film.

As is clear from Table 1, this cured film had extremely high surface resistivity and poor antistatic ability, and also had a large haze value after the taper test, and was poor in abrasion resistance.

Comparative Example 2 The same procedure as Example 1 was carried out except that no inorganic filler was used.

Table 1 shows the results of physical property evaluation of the obtained cured film.

As is clear from Table 1, this cured film had an extremely large haze value after the taper test and poor abrasion resistance, and was also poor in antistatic properties based on the surface resistivity value.

Comparative Example 3 The same procedure as Example 1 was carried out except that no inorganic filler was used and the amount of nonionic antistatic agent was 30 parts by weight.

Table 1 shows the results of physical property evaluation of the obtained cured film.

That is, although this cured film had antistatic properties, it had a large haze value and poor transparency, and also had extremely low abrasion resistance based on the haze value after the taper test.

Comparative Example 4 The same procedure as in Example 1 was carried out except that no inorganic filler was used and the amount of nonionic antistatic agent was 10 parts.

Table 1 shows the results of physical property evaluation of the obtained cured film.

From Table 1, this cured film has a small haze value and excellent transparency, but it has a high surface resistance and poor antistatic performance, and also has a high haze value after the taper test and has poor abrasion resistance. there were.

Comparative examples used untreated fine powder silica (Degus) as an inorganic filler.
The same procedure as in Example 1 was carried out except that SA AEROS I L-380) was used.

Table 1 shows the results of physical property evaluation of the obtained cured film.

As is clear from Table 1, although this cured film had improved antistatic performance, it had a large haze value and poor transparency, and its abrasion resistance was also extremely low based on the haze value after the taper test.

Comparative Example 6 The same procedure as Example 1 was carried out except that the nonionic antistatic agent was not used.

Table 1 shows the results of physical property evaluation of the obtained cured film.

As is clear from Table 1, this cured film has excellent transparency and abrasion resistance based on its haze value and haze value after the taper test, but the surface specific resistance value is large and the antistatic performance is poor. It is extremely inferior.

Procedural amendment April 6, 1986

Claims (1)

[Scope of Claims] [1] A curable composition containing the following components (A), (B), and (C) as essential components. (A) Compound containing two or more acryloyl or methacryloyl groups in the molecule (B) Antistatic agent (C) Inorganic filler whose surface has been treated by hydrolysis of an organosilicon compound represented by the following formula R^1_mR^ 2_nSi(OR^3)_4_-_(_
m_+_n_) [In the formula, R^1 and R^2 are a hydrocarbon residue having 1 to 20 carbon atoms or an organic group having a halogen, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or an amino group, and a Si-C bond R^3 is a hydrocarbon residue having 1 to 6 carbon atoms or an oxygen-containing hydrocarbon residue, m and n are 0, 1 or 2, and (m+n) is 1 or 2. ]