KR820001627B1 - Low friction abrasion resistant coating for transpearent film - Google Patents

Abstract

Abrasion-resistant mottle-free coatings for cinefilm comprise a 0.5-15.0-μ-thick layer contg. >=30 % of a curedepoxy-terminated silane and >=30 % 0.5-25-μ-diam. SiO2 or TiO2 particles with coeff. of friction against Sn-plated steel 0.05-o.30 (ANSI PH 1.47-1972) and dynamic coeff. of friction <0.41 and allow 75 % transmission of the 400-780 nm radiation transmitted by the uncoated film. The coated film possessed good abrasion resistance, optical qualities, and coeffs. offriction and dynamic friction of 0.18 and<0.25, resp.

Description

Transparent video film

The material of the image transparent film is often preserved in a rolled form with a continuous strip for easy use on an individual screen or to obtain a continuous screen. Microfilms are often preserved in the form of bands or rolls for ease of use, and active photographs are provided from rolls or reels that are wound so that the screen can be viewed quickly and continuously. Because these screens need to be imaged to move these screens, the film is often damaged gradually due to wear and scratches caused by mechanical components or hard surfaces that occur during the film's operation.

This phenomenon is especially apparent in activity photography projectors. This scratch can occur on both the image material itself (ie, the developed emulsified layer) or on the film support. Scratches reduce the traction and service life of the film, making it economical. Therefore, it is desirable to protect such films, especially transparent films, to be projected onto the projector from abrasion and scratches.

Recent advances in abrasion resistant coating technology have been published in parts of U.S. Pat.Nos. 3955,035, 4,026,826 and 4,049,861, and more advanced are U.S. Patent Nos. 4,101,513 and March 28, 1977. It is also described in patent application serial number 78,042. According to these patents, silanes of both functional groups (i.e. polymerizable silanes and other groups such as epoxy groups, acryloxy groups (including methacryloxy groups), vinyl groups and amino groups) in forming a wear-resistant coating are described. Compounds having both of them) are used. These monomers all have their own special ideal properties, and the monomers involved in the present invention are silanes in which the terminal group is an epoxy group.

Silanes in which the terminal is an epoxy group include a hydrolyzable divalent aliphatic and aromatic having a polymerizable (preferably terminal) epoxy group and a terminal polymerizable silane group, and these groups having a nitrogen atom and / or an oxygen atom in the bond chain. Or a compound or a substance which is crosslinked as an aliphatic and aromatic hydrocarbon bond. For example, oxygen atoms can be contained in the chain only if they are ether bonds.

Since these substituents on the chain do not have a great influence on the functional group function of the silanes whose terminal is an epoxy group required in the polymerization reaction which consists of a silane group or a terminal group ethoxy group, these bond chains are normally carried out like a well-known technique. Can be substituted. Examples of the substituents that may be contained on the binding moiety or the crosslinking moiety include groups such as NO ₂ , alkyl groups such as CH ₃ (CH ₂ ) n, alkoxy and halogens such as methoxy groups, and the like.

In the structural formula described on the specification of the present invention, it is meant that substitution of the crosslinked component as described above is possible unless indicated as "bivalent unsubstituted hydrocarbon radical".

Examples of good epoxy terminal silanes in practicing the present invention are mixtures having the following structural formula.

Wherein R is less than 20 carbon atoms, non-hydrolyzable divalent hydrocarbon radical aliphatic, aromatic or aliphatic and aromatic containing or 20 carbon atoms consisting of atoms which may be formed in the skeleton of C, H, N, S and O atom divalent radicals Less than divalent radicals and oxygen are bound in ether form. In addition, the skeleton preferably contains only oxygen atoms in addition to carbon atoms. It is most preferable that two hetero atoms cannot be adjacent in the skeleton of the divalent hydrocarbon group, and the hetero atoms of R are not directly bonded to the 1,2-epoxy ring of the structural formula. What was described above is defined about the bivalent hydrocarbon group of the siloxane whose terminal is an epoxy group in the Example of this invention. n value is 0 to 1. R ₁ is an aliphatic hydrocarbon group having less than 10 carbon atoms, an acyl group having less than 10 carbon atoms, or a radical of (CH ₂ CH ₂ O) _k Z, where K is an integer of 1 or more, and Z is hydrogen or carbon atom Less than 10 or an aliphatic hydrocarbon group consisting of hydrogen) and m is 1-3.

-O-CH₂-CH₂-및-CH₂O-(CH₂)₃-등과 같은 에테르기이고, R₁이 메틸, 에틸, 이소프로필, 부틸, 비닐, 알킬 등과 같은 탄소원자수가 10미만인 지방족 탄화수소기이거나 또는 포르밀, 아세틸, 프로피오닐등과 같은 탄소원자수가 10미만의 아실기 또(CH₂CH₂O)_kZ의 라디칼(여기서 K가 1이상의 정수, 즉, 2,5 및 8)이며, Z는 수소 혹은 메틸, 에틸, 이소프로필, 부틸비닐 및 알릴기와 같은 탄소원자소가 10미만의 지방족 탄화수소기이다.The composition used in the present invention, wherein R is a divalent hydrocarbon group such as methylene, ethylene, decalene, phenylene, cyclohexylene, cyclopentylene, methylcyclohexelene, 2-ethyl butylene, albene and the like; or CH ₂ -CH ₂ -O-CH ₂ -CH ₂ , (CH ₂ -CH ₂ O) ₂ -CH ₂ -CH _2- ,

An aliphatic group such as —O—CH ₂ —CH ₂ — and —CH ₂ O— (CH ₂ ) ₃ —, etc., and R ₁ is aliphatic having less than 10 carbon atoms such as methyl, ethyl, isopropyl, butyl, vinyl, alkyl, etc. A hydrocarbon group or an acyl group having less than 10 carbon atoms such as formyl, acetyl, propionyl or the like (CH ₂ CH ₂ O) or a radical of _k Z (where K is an integer of 1 or more, ie 2,5 and 8) Z is hydrogen or an aliphatic hydrocarbon group having less than 10 carbon atoms such as methyl, ethyl, isopropyl, butylvinyl and allyl groups.

As the composition of the present invention, in addition to the silanes described above, hydrolyzates, prepolymers and precondensates of the silanes can also be used.

The hydrolyzate is a form in which some or all of the actual shot OR ₁ groups are hydrolyzed. Thus, the term precondensate refers to siloxanes in which silicon atoms are combined with oxygen atoms. The prepolymer is in the form of polymerized groups other than silanes, as in US Pat. No. 4,100,134.

The most preferable silane whose terminal is an epoxy group is a structure which has a following structural formula.

Where m is 1 to 6, preferably 1 to 4, n is 0 or 1, preferably 1, P is 1 to 6, most preferably 1 to 4, and R ₁ is a hydrogen atom Or an alkyl group having 1 to 10 carbon atoms and most preferably 1 to 4 carbon atoms.

In order to have abrasion resistance, the cured coating of the present invention should contain at least 30% by weight of a silane having an epoxy group. However, other copolymers etc. are also used as needed. Substances that do not destroy the properties necessary for the coating, i.e., transmittance, coefficient of friction, and wear resistance, can usually be mixed into the coating. Additives such as antistatic agents, ultraviolet radiation absorbers (ie, benzophenone and benzotriassool), flow regulators, plasticizers and the like can also be used. The substance which reacts with an epoxy group or a silane group during hardening can also be mixed as needed. Mono and polyepoxides and especially aliphatic mono and poly epoxides are particularly useful in compositions comprising silanes having terminal epoxy groups, since they can improve the flexibility of the coating. This is particularly preferable for the film of the activity photographic film.

Particularly useful polyepoxys as copolymers are usually represented by the following structural formula.

Wherein R ₂ is an aliphatic or alicyclic group, A and B are hydrogen atoms, or atoms required to form a 5 or 6 alicyclic ring upon fusion, q is the valence of R ₂ , preferably 1, 2 or 3, most preferably 2.

Among the above structural formulas, preferred epoxy copolymers may be selected from the following structural formulas.

기이고, A및 B와 A₁및 B₁가 각각 수소 원자 또는 5 또는 6원자로 구성되는 지환족환을 형성하는데 필요한 원자이고, r 및 u가 각각 1에서 6의 정수이며, S가 1에서 6의 정수인 하기 구조식을 갖는 혼합물을 가리킨다.Wherein n is 1 to 6, p + q = 1 or 2, p and q are each 0 or 1, X and Y are each 1) m = 1 or 2, where the terminal carbon atom is directly with the carbon of the epoxy group Having the defect that the thixo atom of the -O-(-(CH ₂ ) n- group or 2) carbonyl group to bond directly bonds with the crosslinking group- (CH ₂ ) n-

A and B and A ₁ and B ₁ are each a hydrogen atom or an atom necessary to form an alicyclic ring composed of 5 or 6 atoms, r and u are each an integer of 1 to 6, and S is 1 to 6 It refers to a mixture having the following structural formula which is an integer.

Alkylene and polyalkylene diols are useful copolymers with the silane reactive materials of the present invention. Diethylene glycol, triethylene glycol, polypropylene glycol, and polyethylene glycol are typical materials of this class. Rings of mass having a molecular weight (ie, 2 to 10 oxyalkylene units) between dietylene glycol and decaethylene glycol or dipropylene glycol and decapropylene glycol are the most preferred of these classes.

Silanes, such as tetraethoxy silane, can be copolymerized with the reactant. As mentioned above, additives and common reactants are only limited in that they do not destroy the properties required for the coating.

Since these substances form the outstanding wear-resistant film, they show a remarkable improvement in this technology. Significant problems are encountered when used on films actuated by mechanical manipulation, especially on photographs of activity that must meet certain mechanical resistances. Since the wear resistant film has a great surface friction, the film image flickers on the screen as a result of "chatter" when the film is activated with a film having a wear resistant film of silane whose end is epoxy. The term " chatter " in the art generally refers to the film moving at too fast or too slow due to frictional drag or too little friction. This phenomenon causes the projected picture to be rolled up or shaken, often causing the device to shake.

Even in ordinary active photographic films that do not use wear-resistant coatings, since the surface friction is so great, it has become common practice in photography to coat all active photographic films with wax to prevent this chatter phenomenon. These waxes give the film a smooth and glossy appearance. When such wax was applied on an activity photographic film having a wear resistant film of silane having an epoxy group at the end, the wax formed a mottled discontinuous film on the surface. This helped to reduce the chatter phenomenon, but it was difficult to use and did not completely eliminate the problem of the chatter phenomenon, thus damaging the appearance of the film. Due to the poor adhesion between the film and the wax, the film quickly became abrasion.

In addition to the requirements for wear-resistant coatings on activity photographic films on the properties of friction, the coatings must also be satisfactory optically. Transparent films with abrasion resistant coatings should have a transmittance of at least 75% for all rays between 400 mm and 800 mm passing through the uncoated film. Preferably it should transmit at least 90% of this light. Since the film can be coated on the acoustic portion of the film projected by infrared radiation, the film with the wear-resistant coating must also have a higher transmittance to the infrared radiation of the acoustic portion.

In order to reduce friction, the composition of the wear resistant coating used or the coating coated thereon must be improved so that a mottled appearance does not occur on the film. In particular, the coating containing the additive must pass the following experiment. It contains an additive used to control the coefficient of friction, and a single layer of transparent glass of 0.3 to 0.4 cm is coated with a wear resistant film whose cured final thickness is about 5 microns. The unencapsulated glass is placed against a hard, smooth white background, and projected onto the film of the Hinbantang with 10 candles / cm 2 illumination.

The stain that forms an absorbance of 0.30 or more (measured with a standard chuck in the stain) in an area of at least 1 mm 2 is too excessive. In the embodiment of the present invention, the term “no stain” is defined as a film forming an absorbance of 0.3 or less by the above experiment (hereinafter, the litzol test). Preferably, 0.1 or less is the most preferable.

In the present invention, the composition of the silanes, which are epoxy groups at the terminal, on the transparent image film has abrasion resistance and lower friction properties, thereby enabling mechanical movement of the film.

According to the present invention, at least one side of the transparent image film is coated with a wear resistant film of 0.5 to 1.50 mu. The cured composition film of the reaction component containing 30 weight% or more of the silane whose terminal is an epoxy group is obtained. This coating has a coefficient of kinetic friction of 0.05 to 0.3 with respect to the smooth tin plated steel surface, and can transmit 75% or more of visible light between 400 and 780 mm through which the uncoated film is transmitted.

The film has a coefficient of kinetic friction of less than 0.41 for the film itself, and the film itself has a transmittance of 75% or more for all visible light and a transmittance of 90% or more for visible light between 400 and 780 mm. Do. In the case where the film is coated on the infrared projected image (i.e., the acoustic portion), the transmittance for infrared radiation is preferably 50% or more, preferably 70% or more. The coefficient of dynamic friction for smooth tin plated steels is preferably between 0.12 and 0.25.

The coefficient of kinetic friction (μ) between the two faces is the force F required to move the first face in contact with the second face to the total force (W) needed to move the two faces together. Ratio. This is independent of the surface area in contact within reasonable limits. (In other words, when the board is pressed against the end of the pin, the frictional drag is generated rather than the dynamic friction coefficient. The definition of the dynamic friction coefficient is expressed as follows.)

The dynamic friction coefficient can be conveniently measured using a sloped device in which the value of mu = tan (θ) (θ is the inclination angle of the plane with respect to the horizontal) is established.

In the present invention, the dynamic friction coefficient was measured using a special apparatus. Tighten on a flat stretched surface that can tilt the surface to be tested (ie, film). Beam-shaped devices are suitable. When the device is attached to one side, the inclination angle appears on the integration chuck. An inverted U-shaped holder (652.6 g in weight) that is large enough to easily open the hair of a beam-like device is a small tin-plated steel wire with a 2 mm radius of curvature attached to the center of the U-shaped member (diameter). Since it is 0.89 mm), it can be extended 22 mm from the member. Because the bend is located in the center of the wire, the U-shaped member can be in equilibrium with the wire. Place the wires against the film sample on the untied side so that the bent wires contact the film. Slowly raise the device, such as a hanging beam, until the movable U-shaped member starts to slide.

The static friction coefficient is the tangent of the angle θ where the U-shaped member first starts to slide. This is repeated 2-3 times to calculate the average value. Each time the bent wire is washed with 1,2-dichloroethane.

It can be measured by a similar method with the same coefficient of friction. The film tilts the beam-like device, and then touches the mobile U-shaped device and starts to move. As the U-shaped member continues to move along the beamlike element, the tilt of the beamlike element is lowered to the minimum angle as long as it continues to move. The sliding speed at these minimum angles is typically about 0.7 m / sec.

The criterion of the coefficient of kinetic friction for the tin-plated steel of the present invention is the same as that obtained using the apparatus.

When measuring the coefficient of friction of the film, the experimented film was bent tightly around the line on the movable U-shaped member. The experiment is continued in the same manner as described above, except that it is fastened appropriately. The sliding speed here was typically 0.25-0.35 m / sec. The criteria for the coefficient of friction between the film and the film are the same as the values obtained in the device.

This experiment is published as an AN test method for measuring the degree of lubrication on photographic film by paper clip friction test, and is known as the technique of ANSI pH 1.47-1972. The experiment is used by National Association-Ice Photography Co., Ltd. and an experimental apparatus is commercially available. Abrasion resistant coating compositions made of these reactive materials of silanes having terminal epoxy groups should be modified to have desirable properties. It was found that coatings made of unmodified epoxy terminated silanes still had too high a coefficient of friction. The two most preferred methods of improvement are the mixing of fines which reduce the contact surface area between the coating and the surface and suitable oligomers or polymerizations which do not destroy wear resistance, do not create stains, do not excessively reduce permeability, and reduce surface friction. To add the substance.

The operation of improving the frictional properties by adding particulate matter to the film can be made relatively simple and inexpensive. Particles should be large enough to affect the appearance of the surface, and should not be large enough, so that no bad visual defects occur in the projected image, and the size of the particles does not spread on the surface of the film. Should be small enough, and the numbers should be sparse. The particle size should be between 0.05-25 microns. Smaller particles can be used, but are usually satisfactory when the particle size is between 20-200% relative to the final film thickness.

The particle size is usually between 25% and 150% of the final film thickness. The size of the microparticles refers to the particles of a separate object separately, and when the microparticles form agglomerates with each other, it means the size of the aggregated itself. Separately separated particles of about 0.01 micron in particle size did not function properly until they formed agglomerates and became 0.1 and 0.2 microns in size. Only by reaching this size did these particles function properly, reducing the surface friction of the coating. The surprising fact is that the composition of the microparticles is relatively insignificant. Opaque substances such as clay particles (ie bentonite) and carbon black can also be used. Particulates do not tend to absorb significantly (unless too many particles are contained) and are of such magnitude that only moderate light scattering occurs.

Particles infiltrated by the coating composition are preferred, in particular thinlica and / or titania elementary particles (30% -100% silica and / or titania).

As mentioned above, it is conceivable that the particles act to reduce the contact surface area between the film and the surface. It is known that the friction coefficient is usually independent of the surface area, but according to the present invention, the friction coefficient can be reduced by reducing the surface area. This is a surprising fact. The contact surface area is measured by applying a flat film coated on a flat smooth glass plate to a pressure of about 20 kg / cm 2. The contact surface area containing particulates is reduced because the particulate matter affects the appearance of the surface. Particulates should not protrude on the surface of the coating and should normally be hidden within the coating. If the particulates are smooth, some protruding particulates may be acceptable but not preferred. Contact surface area should be reduced by more than 15%. It succeeded in reducing the contact area by 98%. Experience has shown that reducing the contact surface area between 40% and 90% yields the best results. The amount to be reduced depends on the desired final properties.

The coating can also be improved by adding oligomers and polymers (preferably 0.01% by weight to 25% by weight, most preferably 0.05% to 15% by weight) which can reduce the coefficient of friction. These oligomers and polymers can be mixed separately on the coating or reacted with each other to form a polymer network with silanes, which are epoxy groups at the ends. Preferred materials for which the coefficient of friction can be adjusted are oligomers and polymers having at least 5% and preferably at least 20% of the siloxane units of the following structural formula.

Here, R ₃ and R ₄ are each a group selected from an alkyl group having 1 to 4 carbon atoms and a phenyl group having 10 or less carbon atoms, and n is an integer of 1 or more.

The phenyl group having 10 or less carbon atoms includes phenyl substituents such as 0-chlorophenyl, toline, p-ethylphenyl, m-cyanobutylphenyl, 3,4-dimethylphenyl, naphthyl and the like. Preferred substituents are meta and para substituents which consist of chlorine, cancellation and alkyl groups having 1 to 4 carbon atoms. More preferred R ₃ and R _{4 are} methyl, ethyl propyl, butyl, phenyl and tolyl, most preferred R ₄ and R ₃ are methyl, ethyl and phenyl, of which ethyl is the least preferred.

Any composition of these polymers or oligomer additives must be mixed with any critical properties either separately from the composition or in combination with other oligomers and additives useful in the examples of the present invention.

It is found that the most useful additives for the present invention are those which pass the suitability test defined above. This experiment is described below. The following experiments will be described even in the case of substances which cause a reduction in friction and moderately reduce friction. There is no contradiction that the passing substances are more preferable than the rejecting substances.

Standard solution of 10% by weight butyrate cellulose acetate (e.g., 0.4 seconds by ASTM D-817-65, such as Eastman-Kodak 553-04, 0.4 seconds by ASTM D-134-56 Poise, acetyl content 2%, butyryl content 47%) was prepared in ethyl acetate. The test substance was dissolved in this solution at a rate of 5% by weight relative to the ethyl acetate component of lactate acetate, and the solution was coated on a terephthalic acid polyethylene pimungung with about 2 microns thick of a line wound with line 8.

The solution was then dried overnight in air and then the coefficient of friction was measured by ANSI pH 1.47-1972 (described below).

The coefficient of friction according to ANSI pH 1.47-1972 is preferably less than 0.3 (preferably less than 0.27) where the sliding speed exceeds 0.5 m / sec.

Experiments using the polymers and experimental procedures defined above are referred to as Zollein experiments.

There are a number of catalyst systems useful for making the coatings of the present invention. In some cases, different catalysts must be used for each step of the reaction. In the curing agent based on silanes whose terminal is an epoxy group, many catalyst materials were used in the prior art, and some of these materials hardened both a silane and an epoxy group.

In U. S. Patent No. 4,049, 861, fluorinated aliphatic sulfonyl and sulfone catalysts were used to cure silanes having terminal epoxy groups.

In US Pat. No. 3,955,035, Lewis and Breensutes acid catalysts were used to cure silanes with epoxy terminated, while US Pat. No. 4,101,513 used onium, i.e., radiation sensitive catalysts, to terminate epoxy groups. Phosphorus silane was cured. Since these all three harden | cure both an epoxy group and silanes, the silane composition whose terminal is an epoxy group is a preferable catalysts. Diazos are catalysts useful for catalysts such as salts, and catalysts other than those for individual groups can also be used in combination with these catalysts.

Reference to the embodiments described below will help to understand the present invention in more detail.

[Example 1-9]

According to these examples it can be seen that the functional group properties are not very good when the compositions and additives of the prior art are used as a film on a film, especially an activity photographic film. In all examples 16 and 35 mm acetate cellulose were used as the substrate of the active photographic film. The abrasion-resistant coating with or without the additive (line 25) was coated on both sides of the film with a rod wound on a line, and then cured overnight at room temperature to form a film having a final thickness of 5.0 탆. In Example 1-8, SbCl ₅ , which is considered to be one of the most effective catalysts among the additive materials published in US Pat. No. 3,955,035, was used.

Table 1 below shows the coefficient of kinetic friction (Cf) for the composition used and the tin-plated steel and the coefficient of kinetic friction (fi) for the film coating itself. In all examples a 10% by weight SbCI5 solution in γ-glycidoxy propyl trimethoxy silane dhf as the silane with the epoxy group at the end and CH ₂ ClCH ₂ Cl as the catalyst was used. The gram number of γ-glycidoxy propyl trimethoxy silane and the weight% of the catalyst (with respect to the silane whose terminal is an epoxy group) used for the following Table 1 are shown. Unless otherwise noted, the cured film coatings had a thickness of about 5 microns in all examples.

TABLE 1

In the above examples, PM is polymethyl methacrylate [15% by weight in (CH ₂ Cl ₂ ) ₂ ], CA is cellulose acetate (10% in methyl ketone), CN is nitro cellulose (isobutyl) 10% in acetate) and LS each represent an organo-silicon liquid consisting of the structure

N and m here represent an integer of 2 or more, where 125 Celtis stokes at Mn = 1500, d = 0.99 and viscosity = 25 ° C.

The content of siloxane units exceeds 20% by weight in the polymer.

Numbers for wear resistance are based on 1-10 scales measured visually after 10 wears at 0.5 kg force with 0000 steel wool of 5 cm 2. The value of 10 remains unchanged. 8 is minimal to the naked eye, scratches 6 can be felt, but moderate scratches, 4 is undesirable, but large naked eye scratches are harmless to the substrate, 2 is harmful to the substrate, and the wear resistance of the film is poor. Each value represents one value.

Polymerization additives disclosed in U.S. Patent No. 3,955,035 through the above examples are not good in the coefficient of friction for tin-plated steel or the film itself, and the wear resistance of the film tends to be significantly reduced. It can be seen that all the reference values are satisfied.

Example 10-13

The following examples describe the use of particulates in wear resistant coatings to reduce the coefficient of friction of the coated film. As a silane whose terminal is an epoxy group, a mixture of γ-glycidoxypropyl trimethoxy silane and 1,4-butanediol diglycidyl ether (60/40 wt%) was used.

을 약 50/50을 비율의 혼합물로 이루어지는 자의 방사선 감수성촉매인 폴리아틸 설포늄 헥사플루오트 안티몬네이트를 사용하였다.As a catalyst (C ₆ H ₅ ) ₃ SSbF ₆ and

The polyacetyl sulfonium hexafluoro antimonate, which is a radiation-sensitive catalyst of a mixture consisting of a mixture of about 50/50 ratio, was used.

In each of the above examples, the wear resistance value and the optical quality for the film were good.

In the above embodiments, LV is aggregated and precipitated silica particles having an average mass size of 3.5 microns, SY is silica particles having a small amount of organic material bonded to the silica particles and having an average mass size of 4 microns. 1.8 and dispersed particle size of 0.8x0.8x0.0025 microns and refer to montmorill onite clay, respectively, metered in trialkyl aryl ammonium.

The size of the individual particles of silica was less than 1 micron.

As can be seen from the above examples, all the properties of the coated film were satisfactory. Although montmorillonite clay is an opaque material, it is interesting to note that the optical properties of silver activity films are good. In each of the embodiments, the transmittance satisfies all the required values.

[Example 14-22]

The above examples use oligomers or polymer additives in wear resistant coatings. The silane whose terminal used in Example 14-22 is an epoxy group is the same as what was used in Example 10-13.

(하기에서는 EP-2라함) 및 디에틸렌 글리코올을 하기 표에 나타낸 글리코올에 대한 실란의 중량 비율의 혼합물을 사용하였다.In Examples 17-19

A mixture of the weight ratio of silane to glycol (hereinafter referred to as EP-2) and diethylene glycol is shown in the table below.

(하기에서는 E-2라함)의 혼합물을 사용하였다. 실시예 22에서는 EP-2, 실시예 1의 에폭시 실란, 디에틸렌 글리코올 및 E-2를 하기 표에 각각 중량비율로 하여 사용하였다. 각 실시예들의 촉매로서는 0.2% 트리아릴설포늄 헥사플루오트안티몬 네이트를 사용하였다. 실시예들 중 첨가제 SF는 하기 구조식을 갖는 소중합체를 가리킨다.In Examples 20 and 21 EP-2 and

(Hereinafter referred to as E-2) was used. In Example 22, EP-2, epoxy silane of Example 1, diethylene glycol and E-2 were used as the weight ratio in the following table, respectively. 0.2% triarylsulfonium hexafluoroantimonate was used as the catalyst in each example. Additive SF in the examples refers to oligomers having the structure

Wherein X is that the viscosity of the oligomer is 45-65 centipoise at 25 ° C. and d = 1.03.

The upper number in the table indicates the coefficient of friction for the cellulose acetate acetate and the lower number the coefficient of friction for the cured gelatin emulsion.

In each of the examples, curing was performed for 2 minutes using a 275 watt solar lamp at a distance of 16 cm from the surface of the coating.

As can be seen from the results described above, the friction characteristics obtained by the embodiments of the present invention were satisfactory. Optical properties and wear resistance were also good in each example. No staining was observed and the transmittance was very good.

Example 23

7.82 g of γ-glycidoxy propyl trimethoxy silane is partially hydrolyzed in ethanol (with 40% methoxy group removed) with hydrochloric acid, having an average molecular weight of about 500 and a (ηD) of 1.399 at 22 ° C. 1.96 g of the polymer obtained by partial addition decomposition of diethoxydimethylsilane (without 50% ethoxy group removed) were mixed. This polymer serves to reduce the coefficient of friction of the final coating. 0.2 g of triarylcellonium hexafluoro antimonate was mixed with this composition, a film was formed, and then irradiated. The optical quality, abrasion resistance and coefficient of friction of the final coating satisfied all the requirements.

Example 24-25

The FC-430 surfactant described in US Pat. No. 4,026,926 was used in the composition as silanes with epoxy groups at the ends. FC-430 is the trade name for the fluoroalkylester surfactant, an oligomer made by 3M Company.

This example describes the effect on the friction characteristics when the above-mentioned surfactant is used in a coating made of silanes having an epoxy group at the end.

을 실시예 10-13의 2중량% 감광성 촉매를 첨가하였다. 이 조성물의 절반에는 0.02중량%의 FC-430을, 다른쪽의 절반에는 0.3중량%를 첨가시켰다. 양쪽 조성물을 초산셀루로어스 필름상에 피막을 만들어 2분씩 자외방사선에 노출시켜 경화시켰다. 양쪽 모두 주석도금강 및 필름 그 자체에 대한 동마찰계수는 0.4를 초과하였다. 미합중국 특허 제4,026,826호에서는 이 계면 활성제를 약 0.01중량%를 사용하고 있다. (즉, 실시예 2) 이 계면활성제로서는 바람직한 마찰 특성을 갖는 피막이 얻어지지 않았다. 이들 실시예들은 물론 본 발명의 범주에서 벗어나는 것이다. 상기에 서술한 물질을 내마모성 피막의 마찰 특성을 감소시키는 물질로서 이 계면활성제를 함유하는 조성물에 첨가했을시, 마찰 특성에 대하여 이동성 필름상에, 특히 활동사진 필름상에 유용한 요구치를 만족시켰다.60% of γ-glycidoxy propyl trimethoxy silane and 40% of

2 wt% photosensitive catalyst of Examples 10-13 was added. To half of this composition was added 0.02% by weight of FC-430 and to the other half of 0.3% by weight. Both compositions were cured by making a film on a cellulose acetate film and exposing it to ultraviolet radiation for 2 minutes. In both cases, the coefficient of kinetic friction for tin-plated steel and the film itself exceeded 0.4. US Pat. No. 4,026,826 uses about 0.01% by weight of this surfactant. (Ie, Example 2) As this surfactant, the film which has a favorable friction characteristic was not obtained. These embodiments are, of course, beyond the scope of the present invention. When the above-mentioned materials were added to a composition containing this surfactant as a substance which reduces the frictional properties of the wear resistant film, the frictional properties satisfied useful requirements on the mobile film, especially on the active photographic film.

Example 26-31

The following examples describe the use of other useful additives to reduce the coefficient of friction for the wear resistant film on the mobile film. A film of all the compositions was formed with a rod wound on the emulsion side of the 35 mm film, and then cured for 8 minutes using a 275 watt ultraviolet lamp in the presence of the radiation-sensitive catalyst of Examples 10-313 to a thickness of about 8 microns. Dried over.

A composition of 6 ratios of γ-glycidoxy propyl trimethoxy silane and 6 ratios of diepoxy used in Examples 24 and 25 was made. 0.2 wt% of the organic silicone liquid used in Example 9 was used together with the following materials. 0.1% carbon black in Example 26, 0.1% titania dioxide in Example 27, 0.5% stearic acid in Example 28, in Example 29,

Where (m, n and x are integers having a viscosity of 320 centistokes at 25 ° C., a molecular weight of 2400 and an OH equivalent of 1200 at 25 ° C.) in Example 30 having 2% of a 20% polyethylene oxide chain In Example 31, 1% sorbitan tristearic acid having a polyethylene oxide chain of 20 units was used for the sorbitan monosurearic acid derivative of. The results are described as follows.

These materials were all effective in reducing the friction coefficient of the wear resistant film of the present invention.

The coating composition of this invention containing the mixture of the linear silane whose terminal is an epoxy group mentioned above, and the alicyclic silane whose terminal is an epoxy group is preferable compositions. Alicyclic comonomers generally tend to increase the flexibility of the final coating required.

[Examples 32-43]

Table 2 below describes the suitability of the materials for this experiment. The materials should pass the ANSI test where the sliding speed is 0.5 cm / sec. That is, it should be at least as good as the quality required as a preferred additive. As in the above-described method, a film of this class of materials was formed to select candidate materials.

TABLE 2

In the second table, each symbol indicates a substance as described above, in addition, QS is a substance having the following structural formula wherein the viscosity is 320 centistokes at 25 ° C., the molecular weight is 2400, the OH equivalent is 1200, and R is an aliphatic group. of,

MS is a 50% hydrolysis product of (CH ₃ ) ₂ Si (OCH ₂ CH ₃ ) 2, KS is (CF ₂ CFCl) n where n is an integer greater than ₂ , NJ is paraffinic oil, SA is stearic acid, PE is polyethyl acrylate, TS is sorbitan monostearate having 20 units of polyethylene oxide chain,

ME represents cyclic tetradimethyl siloxane having the following formula.

As can be seen from the above results, any of the above-described examples having a low coefficient of friction of the wear resistant film failed the required screening experiment.

In the actual results, these additives exhibited good performance for production, but did not function well as the preferred substances that passed the experiment. In Example 43, the substance itself was found to fail the preferred screening experiment. However, when used in combination with other substances, it can be seen that the screening test was passed. Example 40 shows that the sliding speed is 0.1 cm / sec, which fails the preferred screening experiment. It is conceivable that this experiment can be used to accurately select the desired class of substances.

Claims (1)

The composition containing at least 30% by weight of epoxy terminated silane was cured to form a 0.5-15.0 μm spotless wear resistant coating layer on at least one side of the film, the coating layer being measured for tinned steel by ANSI PH 1.47-1972. A transparent image film having a coefficient of friction of 0.05-0.30, having a dynamic coefficient of friction of 0.41 or less relative to the coating layer and having a transmittance of at least 75% of all radiation of 400-780 mm transmitted by an uncoated image film.