JPH04146971A - Antistatic, active energy ray-curable composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. giving a cured coating film excellent in scratch resistance, antistatic properties, and transparency by compounding a polymerizable (meth)acryloyl compd., a polymerizable acidic phosphoric ester, a difunctional (meth)acrylate, and a tertiary amine hardly sol. or insol. in water. CONSTITUTION:A polymerizable compd. having at least two (meth)acryloyl groups in the molecule (e.g. trimethylolpropane triacrylate), a polymerizable acidic phosphoric ester of formula I [wherein R<1> is H or CH3; R<2> is H or a group of formula II (wherein R<3> is H or CH3; and n is 1-5); and m is 1-5] [e.g. di(meth)acryloyloxyethyl phosphate], a difunctional (meth)acrylate contg. a polyalkylene glycol unit [e.g. polyethylene glycol 400 di(meth)adcrylate], and a tertiary amine hardly sol. or insol. in water (e.g. dimethylbenzylamine) are componded to give an active energy ray-curable compsn., which gives a cured coating film excellent in scratch resistance, wet-heat resistance, antistatic properties, and transparency and is useful as the material of a protective film on a reading plane of an optical disc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an active energy ray-curable composition having excellent scratch resistance, antistatic properties, and transparency.

(Prior art) Currently, many synthetic resin molded products are on the market, and although these molded products have many excellent properties, they generally have low surface hardness and low resistance to scratches, so it is difficult to process the product. The surface is easily scratched during shipping and transportation, which not only impairs the product value, but also when removing dirt such as dirt that has adhered to the surface with a cloth while using the product, wiping and scratches may occur. There was a problem that it was easy to occur.

In addition, static electricity is generated on the surface, which attracts dust, resulting in a loss of optical properties such as aesthetic appearance and transparency.

In order to solve these problems, we have developed a method of forming a scratch-resistant film on the surface of synthetic resin molded products, and a method containing surfactants and conductive fillers as antistatic agents on the surface to provide antistatic properties. Attempts have been made to apply .

However, the method for forming the above scratch-resistant film is
The antistatic property is insufficient, and the method of applying a surfactant-containing material has the problem that the antistatic agent is strongly affected by the humidity of the outside air, and the antistatic property disappears over time. Also,
The method of applying a conductive filler-containing material has problems such as loss of transparency.

On the other hand, in the case of coatings that protect the reading surfaces of optical disks such as magneto-optical disks, high levels of scratch resistance, antistatic properties, transparency, and heat and humidity resistance are required in order to achieve the required high reliability. was.

As a coating agent with scratch resistance, antistatic property, and transparency, for example, JP-A-55-86848 discloses a compound having three or more (meth)acryloyloxy groups in one molecule, (meth) ) A coating composition comprising a polymerizable phosphoric acid ester having an acryloyloxy group and an ethanolamine compound, which can form a film having scratch resistance and antistatic properties by irradiation with active energy rays in air. things are listed. Furthermore, JP-A No. 61-73709 discloses that the amount (0,2 ~10% by weight) have been described. Furthermore, in JP-A-1-62316, 2-
A composition containing 0.4 to 10% by weight of hydroxyethyl (meth)acroyl phosphate is described.

(Problem to be Solved by the Invention) However, in all of these compositions, the active hydroxyl group in the polymerizable phosphate ester that acts as an antistatic agent exists as it is, or hydrophilic ethanolamine exists as a counter ion. It had a problem of poor heat and humidity resistance.

That is, these compositions have not reached a satisfactory level as materials for forming protective films on the reading surfaces of optical disks, including magneto-optical disks, which require a high degree of moisture and heat resistance.

The problem to be solved by the present invention is to provide an active energy ray-curable composition that can form a protective film with excellent scratch resistance, antistatic properties, transparency, and heat and humidity resistance.

(Means for Solving the Problems) In order to solve the above problems, the present invention provides (1) a polymerizable compound having at least two (meth)acryloyl groups in the molecule, (2) a general formula (I )R'O0 111; cHt=c-c-o-(CH2), -0-P-OR"H [wherein, R' represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom or the general formula % formula %) (In the formula, R3 represents a hydrogen atom or a methyl group, and n is 1
Represents an integer between ~5. ) represents a substituent represented by
m represents an integer from 1 to 5. ], (3) a bifunctional (meth)acrylate having a polyalkylene glycol unit, and (4) an active energy ray-curable composition containing a tertiary amine that is sparingly soluble or insoluble in water. The present invention provides an active energy ray-curable composition containing a photopolymerization initiator and a photopolymerization initiator.

The polymerizable compound having at least two (meth)acryloyl groups in the molecule used in the present invention is a component that imparts scratch resistance, such as trimethylolpropane tri(meth)acrylate, dipentaerystol. Hexa(meth)acrylate, dipentaerythol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythdol penta(meth)acrylate, alkyl-modified dipentaerythol tetra(meth)acrylate, pentaerythol tri(meth)acrylate , pentaerythol tetra(meth)acrylate,
Examples include tris[(meth)acryloxyethyl coisone anurate, caffrolactone-modified tris[(meth)acryloxyethyl]isocyanurate, and the like. Among these, trimethylolpropane triacrylate is particularly preferred in terms of viscosity and hardness.

The proportion of the polymerizable compound having at least two (meth)acryloyl groups in the molecule is preferably in the range of 50 to 80% by weight of the active energy ray-curable composition of the present invention. If the usage ratio of the polymerizable compound having at least two or more (meth)acryloyl groups in the molecule is less than 50% by weight, the hardness tends to decrease and the scratch resistance tends to decrease, and the usage ratio is 80% by weight. If it exceeds 20%, the proportion of the antistatic imparting agent used decreases, which tends to reduce the antistatic effect, which is not preferable.

The polymerizable acidic phosphoric acid ester represented by the general formula (1) used in the present invention is an antistatic imparting agent, and examples include Eva,
(meth)acryloxyethyl phosphate, di(meth)acryloxyethyl phosphate, (meth)acryloxypropyl phosphate, di(meth)axoroquine furobylphosphate, (meth)acryloxybutyl phosphate, di(meth)acryloxybutyl phosphate, Examples include (meth)acryloquine butyl phosphate. Among these, di(meth)acryloquine ethyl phosphate is preferred in terms of compatibility and antistatic properties.

The proportion of the polymerizable acidic phosphoric acid ester represented by the general formula (1) is preferably in the range of 10 to 20% by weight of the active energy ray-curable composition of the present invention.

The bifunctional (meth)acrylate having a polyalkylene glycol unit used in the present invention is a component that promotes the development of antistatic properties by the polymerizable acidic phosphate represented by the general formula (I), and is, for example, Examples include glycol 400 di(meth)acrylate, polyethylene glycol 600 di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate, and polypropylene gelicol 600 di(meth)acrylate. Among these, polyethylene glyfur 40
0 di(meth)acrylate is preferred in terms of compatibility.

The proportion of the bifunctional (meth)acrylate having a polyalkylene glycol unit is preferably in the range of 5 to 15% by weight of the active energy ray-curable composition of the present invention.

The tertiary amine that is sparingly soluble or insoluble in water used in the present invention is a component that ionically bonds with the active hydroxyl group contained in the polymerizable acidic phosphoric acid ester represented by the general formula (1),
By using a salt that is sparingly soluble or insoluble in water, the moisture and heat resistance is improved. Examples of tertiary amines that are poorly soluble or insoluble in water include tri-n-octylamine, triarylamine, N-methyl-diarylamine, dimethylbenzylamine, 26-lutidine, 2,4-lutidine, 2.
Examples include 5-lutidine, 3,5-lutidine, 2.4.6-collidine, 2.3.5 collidine, and the like. Among these, dimethylbenzylamine is preferred in terms of compatibility and water resistance.

The proportion of the tertiary amine that is sparingly soluble or insoluble in water is preferably in the range of 60 to 90% of the hydroxyl equivalent contained in the polymerizable acidic phosphoric acid ester represented by the general formula (T). The proportion of tertiary amine that is poorly soluble or insoluble in water is determined by the general formula (
If it is less than 60% of the hydroxyl equivalent contained in the polymerizable acidic phosphoric acid ester represented by I), the moist heat resistance tends to deteriorate, and if it exceeds 90%, the antistatic property is low.
This is not preferred because it tends to have poor compatibility.

As the photopolymerization initiator used in the present invention, various photopolymerization initiators and photopolymerization sensitizers used in general ultraviolet curable resins can be used. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, 2-methylbenzoin, benzophenone, Michler's ketone, benzyl, benzyl dimethyl ketal, 2,2-jethoxyacetophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4
-benzoyl-4'-methyldiphenyl sulfide, 3,3°-dimethyl-4-methoxybenzophenone,
1-(4-dodecylphenyl)-2-hydroxy-2-
Methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1
-phenylpropan-1-one, 2-methyl-1-[4
-(Methylthiophenyl)-2-morpholinoprono-1゜2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 2,4゜6-drimethylbenzoyldiphenylphosphine oxide These photopolymerization initiators can also be used in combination with sensitizing aids such as amines.

Examples of sensitizing aids such as amines include 2-dimethylamine ethylbenzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, and isoamyl p-dimethylaminobenzoate. The proportion of these sensitizing aids used is preferably in the range of 0.1 to 10% by weight of the photopolymerization initiator.

The active energy ray-curable composition of the present invention can sufficiently achieve its initial purpose with the above-mentioned component materials alone, but in order to further improve performance, silane coupling may be applied to the extent that the original properties are not changed. Additives such as agents, polymerization inhibitors, and leveling agents can also be used in combination.

Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane.

Examples of the polymerization inhibitor include hydroquinone monomethyl ether, t-butylcatechol, p-benzoquinone, 2.5-t-butyl-hydroquinone, and phenothiazine.

Examples of the leveling agent include "Modaflow" (manufactured by Monosando) and rFc-430J (manufactured by Minnesota Mining and Manufacturing Company).

(Example) Examples and Comparative Examples 1 to 3 Each active energy ray-curable composition having the composition shown in Table 1 was prepared, and this was dried and coated on the reading surface side of a PC board for an optical disc and on a glass substrate. Each coating was applied to a film thickness of 6 to 7 μm, and then heated using a condensing high-pressure mercury lamp (120 W).
/cm) (belt speed = 3 m/min).

Each of the obtained cured films was evaluated according to the following evaluation criteria, and the results are shown in Table 1.

(1) For the cured film formed on the scratch-resistant glass substrate, JIs
Pencil hardness was measured according to K5651-1966.

(2) Antistatic properties A 1 cm wide,
Two electrodes facing each other with an interval of 1 cm were placed, a voltage of 100 V was applied between the electrodes, the value of the current flowing between the electrodes was read, and the surface resistance was measured.

(3) A PC board having a heat-and-moisture resistant cured film was stored in a constant temperature and humidity base layer at 60° C. and 190% RH for 20 hours or 350 hours, and the state of the cured film was observed.

The abbreviations in Table 1 are as follows.

TMP3A: Trimethylolpropane triacrylate C-9012, manufactured by Osaka Organic Co., Ltd.: Fatty acid diacrylate M-325, manufactured by Sartomer Co., Ltd.: Caprolactone-modified tris(acryloxyethyl)in cyanurate PM-2, manufactured by Toagosei Co., Ltd.: Linn, manufactured by Nippon Kayaku Co., Ltd. Acid ethyl diacrylate PE-400
: Polyethylene glycol 400 diacrylate DMBZA dimethylbenzylamine (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 55 Methyl phenyl glyoxylate (manufactured by Nistouffer Co., Ltd.) The film has excellent scratch resistance, antistatic properties, transparency, and moisture and heat resistance, so it can be used as a protective film for reading images on optical discs, etc.
It is useful as a material for forming protective films on various synthetic resin molded products.

Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. (1) A polymerizable compound having at least two (meth)acryloyl groups in the molecule; (2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R ^1 represents a hydrogen atom or a methyl group, R^
2 is a hydrogen atom or a substituent represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^3 represents a hydrogen atom or a methyl group, and n represents an integer from 1 to 5. where m represents an integer of 1 to 5. ] An activity characterized by containing a polymerizable acidic phosphoric acid ester represented by (3) a bifunctional (meth)acrylate having a polyalkylene glycol unit, and (4) a tertiary amine that is sparingly soluble or insoluble in water. Energy ray curable composition. 2. The active energy ray-curable composition according to claim 1, which contains a photopolymerization initiator.