JPS628144A - Coating material and its preparation - Google Patents

Abstract

PURPOSE:To obtain a coating material of which the electrostatic charge characteristic is decreased by forming a polymn. cured layer formed by polymn. curing of a compd. having a specific compsn. on the surface of a substrate. CONSTITUTION:The polymn. cured layer of the compd. contg. >=50% the unsatd. compd. expressed by the formula (I) is formed on the surface of the substrate. In the formula (I), R is a hydrogen atom or methyl group, X is an alkylene group or oxyalkylene group of 1-12C, M is a phosphorus atom or sulfur atom, n is 1-3. The more specific examples of the unsatd. compd. expressed by the formula (I) include the compd. group expressed by the formulas (II)-(IV). Said unsatd. compd. may be used by being mixed with the unsatd. compd. polymn.- curable by electron ray irradiation. Examples of the substrate include a synthetic resin molding and synthetic resin film, raw paper prepd. by paper making and resin-coated paper formed with water-proof resin coating layers on both surfaces of the raw paper.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to spring clothing with reduced electrostatic properties and a method for producing the same.

[Background of the Invention] In recent years, the practical application of synthetic polymer compounds has progressed one after another in conjunction with advances in polymer chemistry, and synthetic polymer compounds have been widely used not only in synthetic fibers but also in synthetic resin building materials and household goods. ing. For this reason, electrostatic disturbances caused by the electrical insulation properties of synthetic polymer compounds have begun to become noticeable, and countermeasures have been strongly desired.

In particular, photographic materials such as photographic paper and film generally consist of an electrically insulating support and a photographic emulsion layer. Electrostatic charges often accumulate due to friction or forced peeling. This accumulated electrostatic charge causes many problems, but the most important one is that the photosensitive emulsion layer is sensitized by the discharge of the accumulated electrostatic charge before processing, and the photographic paper is processed. In some cases, dot-like spots or dendritic or feather-like wire rings are produced. This is what is called a static mark, and the occurrence of static marks significantly impairs the commercial value of the photographic material, and in some cases, the commercial value is completely lost.

Static marks on photographic light-sensitive materials induced by the accumulation of electrostatic charges as described above tend to become more noticeable as the sensitivity of the photographic light-sensitive materials increases and the processing speed increases. Especially recently, the sensitivity of photographic materials has been increasing, and high-speed coating and
In addition, as photographic materials are more likely to be subjected to harsh handling such as high-speed photographing and high-speed automatic processing during use, static marks are more likely to occur. In addition, these accumulated electrostatic charges can cause secondary problems such as dust easily adhering to the surface of the support of photographic light-sensitive materials and making it difficult to obtain a uniform coating layer. Become.

The best way to eliminate these electrostatic disturbances is to improve the conductivity of the material so that the accumulated charge can be quickly dissipated before it reaches its limit and a discharge occurs. It is to do so.

[Prior art and its problems] Conventionally, attempts have been made to utilize various surfactants, polymers, etc. as a method of improving the conductivity of electrically insulating materials such as synthetic resins. For example, U.S. Pat. No. 2,982, 651
No. 3.428.456, No. 3,457,076, No. 3, 454.

No. 625, No. 3,552,972, No. 3,655.3
Surfactants as described in specifications such as No. 87,
or U.S. Patent Nos. 2,882,157 and 2,972.
, No. 535, No. 3,062゜785, No. 3,262,
No. 807, No. 3,514.291, No. 3,615,5
No. 31, No. 3753.716, No. 3.938.99
A method is known in which a binder containing a polymer or the like as described in No. 9 and the like is coated on the surface of a substrate.

However, none of these methods can provide sufficient antistatic ability, and although some are effective when added in large amounts, they do not improve photographic properties, especially when used as a support for photographic light-sensitive materials. They often have adverse effects and cannot be used, and since water or solvents are used as diluents to apply these materials, a drying step is always required. A single type hot air dryer is generally used for drying, but this requires a large amount of thermal energy.

There is a problem in that the faster this drying process is made, the more equipment space is required, which is unfavorable in terms of equipment design.

Recently, a technique has become known in which certain types of 7-acrylates and methacrylates are polymerized and cured to form a film by irradiating them with electron beams.

This method makes it possible to form a coating layer without using a solvent. Therefore, since the above drying process can be made unnecessary, if the coating layer to be formed has antistatic ability, energy and equipment space problems can be solved while the antistatic ability can be improved. becomes possible. However, since ordinary 7-acrylate and methacrylate polymers are electrically insulating materials, the problem of static electricity accumulation is not solved at all.Also, the above-mentioned surfactants and polymers are added to 7-acrylate and methacrylate and cured with electron beam. Although this method is conceivable, the results are similar to those using a normal binder, and a satisfactory effect cannot be obtained.

[Object of the Invention] The first object of the present invention is to provide a coated product with reduced chargeability and a method for producing the same.

A second object of the present invention is to provide a support for photographic light-sensitive materials in which the antistatic properties of photographic light-sensitive materials are improved without impairing photographic properties, and a method for producing the same.

A third object of the present invention is to provide a support for photographic light-sensitive materials that enables the use of energy-saving and compact equipment and has an antistatic ability, and a method for producing the same.

[Summary of the Invention 1 The object of the present invention is to provide a charging method characterized in that a polymerized and cured layer of a composition containing 50% by weight or more of an unsaturated compound represented by the following general formula (I) is formed on the surface of a substrate. Coated material with reduced properties (I) However, R: hydrogen atom or methyl group X: CHN
Cl2(7) alkylene group or oxyalkylene group M niline atom or sulfur atom n:l, 2. Or 3.

[Effects of the Invention] Since the coating provided by the present invention has reduced chargeability, the occurrence of various undesirable phenomena due to accumulation of static electricity is significantly reduced.In particular, the coating provided by the present invention When the support is a photosensitive support such as a photographic paper support, effects of extremely high practical value such as a marked reduction in the occurrence of static marks can be achieved.

[Detailed Description of the Invention] The coated article with reduced chargeability of the present invention has a polymerized and cured layer formed on the surface of the substrate by polymerizing and curing a composition having a specific composition as described above. It is characterized by

Specific examples of the unsaturated compound represented by the general formula CI) include compounds represented by the following three formulas.

9 (3) R CH2=C-C0O-X-0 However, in each of the above formulas, R is H or CH3,
X is a fullkylene group of CI '''CI2 or
□Oxyalkylene group, and M represents P or S. In each formula, X is particularly an alkylene group such as c or Na3, among which 01 to C3 are most preferable, and an oxyalkylene group is an oxyethylene group. ,
Any one of an oxypropylene group, an oxybutylene group, and an oxystyrene group is preferable, and among these, an oxyethylene group and an oxypropylene group are preferable.
The number of moles of these groups added is preferably about 1 to 2 moles,
Moreover, as M, P (phosphorus atom) is most preferable.

The above-mentioned unsaturated compounds may be used in combination with other unsaturated compounds (preferably unsaturated compounds that can be polymerized and cured by electron beam irradiation).

Examples of unsaturated compounds that can be used in combination include unsaturated organic compounds that have one C=C double bond in one molecule (e.g., acrylic ester, late methacrylic ester, ether acrylate), unsaturated organic compounds with 3 C=C double bonds (e.g. esters, ethers, epoxies, urethane diacrylates or dimethacrylates), unsaturated organic compounds with 3 C=C double bonds in one molecule Compounds (e.g. esters, ethers, epoxies, urethane triacrylates or trimethacrylates)
, unsaturated organic compounds having one C=C double bond and one epoxy group in one molecule (e.g., unsaturated organic compounds having an epoxy group (e.g., epoxy acrylate, epoxy methacrylate) can.

However, when used in combination with other unsaturated compounds in this way, the unsaturated compound of general formula CI) must be present in the coating composition in an amount of 50% by weight or more, and especially 70% by weight or more. If the amount is less than 50% by weight, sufficient antistatic effect will not be exhibited.

A small amount of organic solvent may be added to the above coating composition in order to adjust the viscosity of the coating composition and improve coating suitability. Examples of the organic solvent include acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone and cyclohexanone: methyl acetate, ethyl acetate, butyl acetate, ethyl lactate,
Esters such as acetic acid glycol monoethyl ether; Glycol ethers such as ether, glycol dimethyl ether, glycol monoethyl ether, and dioxane; Aromatic hydrocarbons such as benzene, toluene, and xylene: methylene chloride, ethylene chloride, carbon tetrachloride, chloroform, ethylene Chlorinated hydrocarbons such as chlorohydrin and dichlorobenzene can be selected and used.

Furthermore, flexibility and heat resistance can be imparted to the polymerized and cured layer formed by adding a resin as shown below to the coating composition in advance.

Cellulose esters, polyvinyl butyral, polyvinyl acetate, vinyl acetate copolymers, saturated and unsaturated styrene-unpolyester resins, styrene-containing acrylate copolymer resins, polystyrene resins.

Incidentally, when the purpose is to obtain a photographic light-sensitive material support with reduced chargeability, the following embodiments are used.

Especially images obtained using photographic materials.

There are cases where observation is performed using transmitted light and cases where observation is performed using single reflected light. In the latter case, especially in the case of photographic paper, it is desirable that the support be opaque and have as high a reflectance as possible. For this purpose, an inorganic white pigment may be incorporated into the compound of the present invention.

As the inorganic white pigment, those conventionally used for hiding photographic paper or those that have been proposed can be used. Examples include titanium dioxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, lithopone, alumina white, zinc oxide, silica, antimony trioxide, titanium phosphate, and the like. These can be used alone or in combination.

As an inorganic white pigment, titanium dioxide is particularly preferred because it has a large hiding power.Titanium dioxide may be of the rutile type or anatase type, and they may be used alone or in combination. , those made by the sulfuric acid method and those made by the chlorine method are also acceptable as titanium dioxide.

Surface coating treatment with inorganic substances such as hydrated alumina treatment and hydrated silicon dioxide treatment, trimethylolmethane,
Trimethylol ethane, trimethylol propane, 2.
Those whose surface has been coated with alcohol such as 4-dihydroxy-2-methylpentane or those which have been treated with siloxane can be used as appropriate.

The average particle size of the inorganic white pigment is preferably larger than 0.1 pm, and particularly preferably larger than 0.151 Lm.

When forming the white pigment-containing resin layer, a coating liquid of a composition consisting of the above-mentioned binder component (unsaturated compound and optionally resin) and an inorganic white pigment is prepared, and this coating liquid is applied to the surface of the substrate. The ratio (weight ratio) of the binder component to the inorganic white pigment is preferably in the range of 3/1 to 1/9, particularly preferably in the range of 2/1 to 174.

In addition, in addition to the inorganic white pigment, known additives for photographic paper supports, such as blue, purple, and red pigments, can also be used in combination, if desired.

The above composition for forming a white pigment-containing resin layer can be cross-dispersed using a known mixer to form a coating liquid.

Examples of the substrate in the present invention include synthetic resin molded products and synthetic resin films (including plates and sheets), such as cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, and polyethylene terephthalate film. , polycarbonate film, polyethylene film, polypropylene film, and laminates thereof. Further examples include base paper prepared by papermaking and resin-coated paper in which waterproof resin coating layers are formed on both sides of the base paper.

The material for the base paper can be selected from known raw materials for supports. Examples include paper made from natural pulp, paper made from synthetic pulp made from synthetic resin materials such as polyethylene or polypropylene, paper made by mixing natural pulp and synthetic pulp, or paper made by mixing natural pulp and synthetic pulp. Various types of paper are used.

Moreover, as mentioned above, those having a polyolefin layer such as polyethylene or polypropylene formed on the surface of these base papers (so-called resin-coated paper) can also be used.

The antistatic resin layer formed on the surface of the coating of the present invention may be provided directly on the base paper, or may be provided on the polyolefin layer provided on the surface of the base paper.

It may be provided between the base paper and the polyolefin layer.

These supports are selected from transparent and opaque supports depending on the intended use of the photosensitive material.

Methods for applying the above-mentioned coating liquid for forming antistatic ability of the present invention to a substrate include, for example, air doctor coating,
Blade coat, air knife coat, squeeze coat,
Conventionally known coating methods include impregnation coating, reverse roll coating, transfer roll coating, gravure coating, kiss coating, cast coating, spray coating, and spin cord.

The thickness of the coating layer is generally 0.5 to 100 #Lm, preferably 1 to 50 JLm. Outside this range, uneven coating may occur, a large amount of energy is required for curing, and curing is likely to be insufficient. After surface treatment such as corona □ treatment in advance, the coating solution may be applied to a □ cloth.

The coating liquid applied onto the substrate is polymerized and cured by electron beam irradiation. Electron beam polymerization can be carried out using a conventionally known electron beam accelerator.

Electrons accelerated by an accelerator are applied to the coating layer.
□A radical polymerization reaction occurs.

A curtain beam system can be used, but is preferable.
The i5 electron beam accelerator is a Pandegraaf scanning method, a double scanning method, or a curtain beam method which is relatively inexpensive and can provide a large output. As for the electron beam characteristics, the accelerating voltage is 1:100 to 100.
OKV, preferably 100 to 300 KV, and the absorbed dose is 0.5 to 20 megarads, preferably 2 to 300 kV.
This is lO Megarad. ``It is desirable that the oxygen concentration during irradiation is 5000 ppm or less.

Goni:22t2m::::=Goni l:i(I,::2:
2. The surface can also be matted using a pine trol. In the case of supports for photographic light-sensitive materials, the surface of the cured layer may be subjected to surface treatment such as corona treatment in order to improve adhesion to the photographic emulsion layer, or the surface of the cured layer may be coated with an undercoat. Layers may be provided.

When the coated product of the present invention is used as a support for photographic paper, 1. On the coated product, a silver halide/gelatin-based light-sensitive emulsion layer, an inorganic or organic photoconductive layer, a diazo compound/photosensitive layer, etc. By forming a transparent resin layer or the like, a photographic light-sensitive material can be obtained.

Hereinafter, the present invention will be explained in detail using a support for photographic paper as an example, but the present invention is not limited thereto. Evaluation was made by measuring the surface resistivity using the method described above and observing the occurrence of static marks.

(a) Measurement of surface resistivity The support was sandwiched between brass electrodes with an electrode spacing of 0.14 cm and a length of loc (stainless steel was used for the part in contact with the sample piece). Electrometer manufactured by Takeda Riken: TR-86
51, the current value was read after 1 minute of energization, and the smaller the 0 surface resistance value, the surface resistivity calculated according to Ohm's law, the better the antistatic property.

(b) Observation of static marks A sample piece coated with a silver halide color emulsion on one side of the support was passed between urethane rubber rollers rotating at a speed of 100 m/min in a dark room, and then developed. Observe static marks.

Ranked as follows:

Technique: No static marks were generated on the emulsion surface ■: Static marks were generated on a part of the emulsion surface ■: Static marks were generated on almost the entire emulsion surface [Example 1] Both sides had a thickness of 307 mm The following unsaturated compounds (liquids) A, B, and C were applied to one side of base paper (thickness 180 gm) coated with polyethylene (180 gm) without using a solvent.
The coated layer was then cured by irradiation with an electron beam at an acceleration voltage of 200 kV and an absorbed dose of 10 megarads in a nitrogen atmosphere (oxygen concentration 300 ppm) to obtain a photographic support. The thickness of the cured layer was 5 JLm.

The photographic light-sensitive material support thus obtained was heated at 25°C.
After conditioning the humidity at 60% RH for 2 hours, the resistivity of one side of the cured layer was measured.

Next 3i! Corona discharge treatment was performed on the polyethylene coated surface opposite to the coated surface at a discharge output of 4 kW and a discharge processing speed of 100 m/min, and then a silver halide color photographic emulsion was coated on this surface. The obtained photographic paper was heated to 30% at 25°C.
After conditioning the humidity at RH for 2 hours, a test was conducted to observe the presence or absence of static marks.

H Unsaturated compound A: CH2-GHCOOGHzCH
20-P = I0 unsaturated compound C: CH2CHCOO
CH2Ckh,0CH2-CHCOOCH20H20-
P Gourd 0CH2-CHCOOCHzCH20 The results are shown in Table 1.

[Comparative Example IJ A sample was prepared in the same manner as in Example 1 except that the unsaturated compound in Example 1 was changed to the unsaturated compound shown below, and the surface resistivity and the presence or absence of static marks were tested. .

cn2-cncoosoC3)! 6 o) -- ocn, but l soil layer + n = 3 The results are shown in Table 1.

Table 1 Unsaturated Compounds Surface Resistivity (Ω) Sudafukumark A 5X106 IB
lX107 IC3X 107
1 D 5 X 10 L4 m The results shown in Table 1 show that the photographic material obtained using the coating according to the invention has an excellent antistatic effect.

Furthermore, when the color photographic properties of the photographic paper obtained in the above examples were examined, the photographic properties such as sensitivity fog were good.

Claims (1)

[Claims] 1. A product with reduced chargeability, characterized in that a polymerized and cured layer of a composition containing 50% by weight or more of an unsaturated compound represented by the general formula (I) is formed on the surface of the substrate. Coated material: ▲Mathematical formulas, chemical formulas, tables, etc.▼--(I) However, R: hydrogen atom or methyl group X: alkylene group or oxyalkylene group of C_1 to C_1_2 M: phosphorus atom or sulfur atom n: 1, 2 or 3. 2. The coating material according to claim 1, wherein the composition consists essentially of an unsaturated compound represented by general formula (I). 3. The coated product according to claim 1, wherein R is a hydrogen atom. 4. The coated product according to claim 1, wherein M is a phosphorus atom. 5. The coated article according to claim 1, wherein the surface of the substrate is made of synthetic resin. 6. The coated product according to claim 5, wherein the synthetic resin is a polyolefin resin. 7. The coated product according to claim 1, wherein the substrate is resin-coated paper. 8. The coated product according to claim 7, wherein the resin-coated paper is a support for photographic paper. 9. Forming a coating layer of a composition containing 50% by weight or more of an unsaturated compound represented by general formula (I) on the surface of a substrate, and then polymerizing and curing the coating layer by irradiating the coating layer with an electron beam. Manufacturing method for coatings characterized by: ▲Mathematical formulas, chemical formulas, tables, etc.▼---(I) However, R: hydrogen atom or methyl group X: C_1 to C_1_2 alkylene group or oxyalkylene group M: phosphorus Atom or sulfur atom n: 1, 2, or 3. 10. The method for producing a coating material according to claim 9, wherein the composition consists essentially only of the unsaturated compound represented by the general formula (I).