JPS61118413A - Photosetting coating composition - Google Patents

Abstract

PURPOSE:The title composition that is composed of a specific amount of a specific component such as alkylhydantoin bisepoxide (meth) acrylic acid adduct and a photopolymerization initiator, thus rapidly giving a coating films of good antifogging, antistatic and high durability by irradiation with ultraviolet rays. CONSTITUTION:The objective composition is obtained from (A) 10-80 pts. wt., preferably 20-70 pts. wt. of an alkylhydantoin bisepoxide (meth) acrylic acid adduct of formula I (R1, R2 are H, 1-6C alkyl; R3 is H, methyl) such as 5-isopropylhydantoin bisepoxide (meth) acrylate adduct, (B) 5-70 pts. wt., preferably 10-60 pts. wt. of a (meth) acrylic ester bearing ethylene oxide chains such as hydroxyethyl (meth) acrylate. (C) 0.5-20 pts. wt., preferably 1-10 pts. wt. of (meth) acrilic quaternary ammon-ium salt of formula (II) (R4 is H, methyl; R5 is 2-4C alkylene; R6, R7, R8 are 1-20C alkyl; Y<-> is Hydroxyl, chlorine ions) and (D) 0.5-5 pts. wt., based on 100 pts. wt. of the total components A, B and C, of a photopolymerization initiaor.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photocurable coating composition that forms a film with excellent antifogging and antistatic properties.

Plastic materials are generally used in a wide range of industries as transparent substrates because they are easy to manufacture, can be supplied in large quantities at low cost, and have excellent properties such as water resistance, chemical resistance, impact resistance, and electrical insulation. It is widely used in the field. However, the drawbacks of such general-purpose plastic transparent materials are:
The surface has poor hygroscopicity and is highly electrostatic, so transparency itself is lost due to clouding that occurs when the surface temperature drops below the dew point of the environment, and dust adhesion due to the generation of static electricity, which is a major inconvenience during use. Sometimes I feel that.

As a means to prevent such drawbacks, research has been conducted into coating materials that form a cured film with excellent antifogging and antistatic properties on the surface of transparent plastic materials, and various coating methods have been attempted. However, while the coatings formed using conventional coating materials are somewhat satisfactory in terms of antistatic properties, they still have drawbacks such as poor antifogging properties and durability, as well as significant increases in processing costs. As a result, it has not been put into practical use, and at present only a small amount of coating material is used.

Therefore, an object of the present invention is to provide a coating composition that can rapidly form a cured film having excellent antifogging properties, antistatic properties, and durability by irradiation with light such as ultraviolet rays. .

As a result of intensive research into obtaining a film that cures rapidly and has excellent antifogging properties, antistatic properties, and durability, the present inventors found that
A composition comprising an alkylhydantoin bisepoxide (meth)acrylic acid adduct, a (meth)acrylic ester having an ethylene oxide chain, and a (meth)acrylic quaternary ammonium salt, and a photopolymerization initiator added thereto. It was discovered that the coating can be rapidly cured by irradiation with light such as ultraviolet rays on the object to be coated, forming a coating with excellent antifogging properties, antistatic properties, and durability.

That is, the present invention has the following formula: Alkyl hydantoin bisepoxide (meth)acrylic acid adducts 10 to 8011 as shown
1 part (B) 5 to 70 parts by weight of (meth)acrylic acid ester having an ethylene oxide chain and (C) general formula (2) [wherein R1 is hydrogen or a methyl group, R6 is a carbon number of 2 to 20 alkylene mira, R'', R' and R
a represents an alkyl group having 1 to 20 carbon atoms, which may be the same or different, Y-haOH-, C1, Br.

soV, No, , CmHzmISO,-(rn
c1~30) W number) w (cnH*no)zP
0.5 to 20 parts by weight of a (meth)acrylic quaternary ammonium salt represented by O (representing a group selected from the group consisting of n is an integer of 1 to 3) and a photopolymerization initiator. The composition of the present invention is a photocurable composition that can form a cured film with excellent antifogging and antistatic properties by irradiating it with ultraviolet rays in the air. Not only does it provide excellent anti-fog and anti-static properties to the coating formed using this method, but it also provides a hardened coating that is excellent in terms of practical processing such as wear resistance and surface smoothness, so it can be used for plastic materials and other applications such as those listed below. It can be widely used as a coating material for products.

(I) Electrical and electronic related parts such as computer rooms and ICs, flooring materials, and wall materials.

(2) Flooring and wall materials for medical facilities such as operating rooms.

(3) Optical products such as plastic lenses, resin mirrors, and organic reflectors.

(4) Products related to office decoration such as displays, name plates, dust cover cases, etc.

General formula (I) of the component (A) used in the composition of the present invention
Specific examples of compounds represented by ) include 5-isopropylhydantoin bisepoxide (meth)acrylic acid adduct, 5,5-dimethylhydantoin bisepoxide (meth)acrylic acid adduct, etc.0 These alkylhydantoin The method for producing the bisepoxide (meth)acrylic acid adduct is, for example, based on the known method described in Japanese Patent Publication No. 31472/1972, using 5,5-dialkyl or 5-dialkyl.
It is produced by the addition reaction of monoalkyl hydantoin bisepoxide and (meth)acrylic acid. These adducts can be used alone or in combination of two or more within the composition range.

Specific examples of the (meth)acrylic acid ester having an ethylene oxide chain as the component (B) used in the present invention include hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate,
-meth)acrylate, polyoxyethylated trimethylolpropane tri(meth)acrylate, polyoxyethylated pentaerythritol tetra(meth)acrylate, polyoxyethylated dipentaerythritol hexa(meth)acrylate, and the like. If the number of H, -CHl-0 in the chain + contained in one molecule of these (meth)acrylic esters having an ethylene oxide chain exceeds 20, the reactivity of the vinyl group in the molecule decreases and curing becomes difficult. If it is insufficient, the hardness of the coating will also decrease.
The preferred number range is 1 to 20. The method for producing (meth)acrylic acid esters containing ethylene oxide chains is to add ethylene oxide to (meth)acrylic acid using the usual esterification method, or to add (meth)acrylic acid to the corresponding alcohol to which ethylene oxide has been added. made by esterification of

One of these (meth)acrylic acid esters can be used alone, but two or more types may be mixed within the composition range.

Specific examples of the compound represented by the general formula (2) of the component (C) used in the present invention include (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltrimethylammonium chloride,
Examples include acryloyloxyethyltrimethylammonium bromide, (meth)acryloyloxyethyltrimethylammonium methyl sulfate, and methods for producing these (meth)acrylic quaternary ammonium salts are known, for example, in JP-A-52-31016. It is produced by reacting N,N-dialkylaminoalkyl (meth)acrylate with a quaternizing agent such as an alkyl halide or a sulfuric ester. One type of these compounds can be used alone, but two or more types may be mixed within the composition range. In the present invention, the above-mentioned (A), (B) and (C) components each have a content of 10 to 80%. Parts by weight, 5 to 70 parts by weight and 0
．． Proportion of 5 to 20 parts by weight (however, the total is 100 parts by weight)
or more preferably 20 to 70 parts by weight, 10 to 6 parts by weight, and 1 to 10 parts by weight, respectively. If component (A) is used in an amount exceeding 80 parts by weight, the anti-scratch performance and surface smoothness of the cured film will be significantly reduced.
If the amount is less than parts by weight, film forming properties will be poor. (B) component is 70
Exceeding the weight part causes a decrease in adhesion to the coated object due to surface roughening. In addition, if less than 5 parts by weight, the surface flatness of the cured film decreases, and if it exceeds 20 parts by weight, the adhesion between the cured film and the object to be coated becomes poor.
If the amount is less than 1 part by weight, the antifogging performance and antistatic performance of the cured film will deteriorate significantly, which is not preferable.

The method of forming a hardened film by irradiating ultraviolet rays is
This method is very preferable from a practical point of view compared to methods using other active energy rays such as electron beams and radiation. However, when using ultraviolet rays as energy rays for curing the coating, In addition to the number, it is necessary to add a photopolymerization initiator that can cause a polymerization initiation reaction by irradiation with ultraviolet rays ◎The photopolymerization initiator used in the present invention is Various known components can be used without particular limitation as long as they are compatible with the main components blended with component C). Specific examples of such photopolymerization initiators include benzoin, benzoin methyl ether,
Carbonyl compounds such as benzoin ethyl ether, benzophenone, jetoxyacetophenone, P-chlorobenzophenone, P-methoxybenzophenone, acetophenone, trichloroacetophenone, sulfur compounds such as tetramethylthiuram monosulfide, do, tetramethylthiuram disulfide, Examples include azo compounds such as azobisisobutyronidotyl and azobis-2,4-dimethylvaleronitrile, which may be used alone or in combination of two or more. Although the amount of photopolymerization initiator used is not particularly limited, it is usually
It is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on a total of 100 parts by weight of components J t (B) and (C). If the amount is 0.1 part by weight, the sensitivity of the composition to ultraviolet rays is insufficient, and if it exceeds 10 parts by weight, the cured film may be colored or the weather resistance may be deteriorated, which is not preferable.

The photocurable coating composition of the present invention which forms a film with excellent antifogging and antistatic properties does not normally use a diluting solvent, but a diluting solvent may be used if desired. Solvents used for this dilution include lower alcohols such as methanol, ethanol and propanol-butanol, lower alkyl cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, lower alkyl esters such as ethyl acetate and butyl acetate, methyl ethyl ketone, Examples include lower alkyl ketones such as methyl isobutyl ketone, which can be used alone or as a mixed solvent. The composition of the present invention can be used with polymethyl methacrylate, polycarbonate, polystyrene, polyvinyl chloride,
It can be applied to plastic base materials such as pickled ester, polyamide, and cellulose.

In coating the object to be coated with the composition of the present invention, commonly used methods such as dipping, spraying, roller coating, flow coating, etc. can be used. After that, by irradiating the film with ultraviolet rays for 5 to 15 seconds in air at room temperature, a cured film with excellent antifogging and antistatic properties can be obtained.

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

Performance evaluation of the film was performed using the following method.

Regarding the appearance, the presence or absence of uneven coating and coloring was examined with the naked eye.

The antifogging property was measured by taking out a film-formed polymethyl methacrylate sample plate maintained at -10°C in an atmosphere of 24°C and 60% RH, and checking for the presence or absence of fogging that occurred at that time. It should be noted that the untreated polymethyl methacrylate plate, that is, without a coating, developed cloudiness over the entire surface. 1. Antistatic property was evaluated by measuring the surface resistivity under conditions of a temperature of 20° C. and a relative temperature of 40%. In addition, the untreated polymethyl methacrylate envy's cause is
+-Kai Kazuhisa hTlr7 was 10140 or more.

The method for measuring adhesion is to make 1m square goblets on the coating surface on a polymethyl methacrylate plate using a steel knife.
00 pieces, strongly stick cellophane adhesive tape (product name: "Cellotape", manufactured by Nichiban Co., Ltd.), and rapidly peel off in a 90 degree direction, and indicate the number of goblets that do not peel off among the 100 goblets. did.

Examples 1 to 4'' and Comparative Example 1 (I) Preparation of composition curing liquid (X-1) contains 40 parts by weight of 5-isopropylhydantoin bisepoxide acrylic acid adduct, polyethylene glycol diacrylate (oxyethylene group 9 h) To a mixed solution of 30 parts by weight and 28 parts by weight of hydroxyethyl acrylate (oxyethylene group = 1 group), 2 parts by weight of acryloyloxyethyltrimethylammonium chloride and 3 parts by weight of 2,2-jethoxyacetophenone were further added. Prepared by thorough stirring and dissolution Other compositions (X-2 to X-5) were also prepared as shown in Table 1 in the same manner as the above composition (X-1).

(2) Coating A small amount of flow control agent is added to each composition prepared as described above, and the coating solution is diluted with impropatur so that the total components are 50 to 80% by weight. Polymethacrylate board (20011XI
0QllX31111) by a casting method and dried for 15 minutes at room temperature to remove the solvent to obtain a film.The film on the sample plate was then heated with an 80 W/am ozone lamp/
10c inside concentrating ultraviolet irradiation device with light and collector tip! 1. The film was cured by irradiating ultraviolet light while moving the conveyor at a speed of 6 rr/min. .

The performance results of the coatings are summarized in Table 2.

w4 oaAp: 2,2-diethoxyacetophenone procedural amendment (voluntary) September 13, 1985

Claims (1)

[Claims] 1. (A) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. Alkyl hydantoin bisepoxide (meth)acrylic acid adducts 10 to 8, where R^3 represents hydrogen or a methyl group)
0 parts by weight (B) 5 to 70 parts by weight of (meth)acrylic acid ester having an ethylene oxide chain and (C) General formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the formula, R^4 is Hydrogen or methyl group, R^5
is an alkylene group having 2 to 20 carbon atoms, R^6, R^7 and R^8 are an alkyl group having 1 to 20 carbon atoms, which may be the same or different, Y^- is OH^-, Cl^-, Br^-,
SO^-_3, NO^-_3, C_mH_2_m_+_
1SO^-_4 (m is an integer from 1 to 3), (C_n
0.5 to 20 parts by weight of a (meth)acrylic quaternary ammonium salt represented by H_2_nO)_2PO^- (representing a group selected from the group consisting of n is an integer of 1 to 3) and photopolymerization A photocurable coating composition comprising an initiator.