JPH03297646A - Slippery film - Google Patents

Abstract

PURPOSE:To obtain a slippery film free from falling of particles and scratch defect by providing a composite layer which has both organic particles having a shell-core structure of dimension specified in means particle diameter and water-soluble or water-dispersible resin as a main component on at least one side of a biaxially oriented film. CONSTITUTION:A slippery film is constituted by providing a composite layer which has both organic particles having a shell-core structure of 0.002-8.0mum mean particle diameter and water-soluble or water-dispersible resin as a main component on at least one side of a biaxially oriented film. When the mean particle diameter D is smaller than 0.002mum, slip properties are insufficient. On the other hand, when it is larger than 8.0mum, this case is not preferable because falling of particles is remarkable. When D/T being the ratio of mean particle diameter D of the organic particles and thickness T of the composite layer is regulated within a range of 1.1-80, slippery properties are more enhanced. Further this case is made more preferable because falling of particles is not remarkable. In such a way, since the particles having the shell-core structure are utilized, a flaw and a while spot are drastically reduced without deteriorating slip characteristics. The film good in the surface state can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a slippery film that has excellent adhesion and is resistant to scratches when the films are rubbed together.

[Conventional technology]

Conventionally, composite films exhibiting slipperiness have been produced by applying a composition containing a roughening substance, polyurethane, acrylic resin, and aliphatic amide as main components (Japanese Unexamined Patent Publication No. 63-1949).
48), and one coated with a composition containing polyurethane, a low molecular weight polyolefin wax, and a surface roughening substance as main components (Japanese Patent Laid-Open No. 109830/1983) is known.

[Problem to be solved by the invention]

However, the conventional laminated film described above has the following problems.

That is, there are problems such as (1) the particles fall off and become attached foreign matter, and (2) the fallen particles cause scratch defects on the film.

The object of the present invention is to improve such problems and provide an easily slippery film free from particle shedding and scratch defects.

[Means to solve the problem]

(1) A composite material containing organic particles having a shell-core structure with an average particle size of 0.002 to 8.0 μm and a water-soluble or water-dispersible resin as main components on at least one side of a biaxially stretched film. A slippery film characterized by providing a layer, (2) an average particle diameter (D) of the organic particles and a thickness (D) of the composite layer;
The slippery film according to claim 1, characterized in that the ratio (D/T) of T) is in the range of 1.1 to 80, (3) characterized in that the composite layer is stretched. The easily slippery film according to claim 1, (4) the easily slippery film according to claim 1, wherein the shell portion of the organic particles is softer than the core portion, (5) the organic particles. The glass transition temperature Tgs of the shell part of
is 50°C or less, and the glass transition temperature Tg of the core portion is
The gist of the invention is the easily slippery film according to claim 1, characterized in that c is higher than Tgs.

In the present invention, the resin constituting the biaxially stretched film includes polyolefin resins such as polypropylene and polyethylene, polyester resins such as polyethylene terephthalate, fluorine resins such as polyphenylene sulfide, polyether ether ketone, and polyvinylidene fluoride. Examples include polyester resins, polyamide resins such as nylon 6, and acrylic resins such as polymethyl methacrylate, among which polyester resins are easy to stretch after forming a composite layer. , is particularly suitable.

Examples of polyester resins include known ones, specifically terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, bis-α, β(2-chlorophenoxy)ethane-4
, 4'-dicarboxylic acid, adipic acid, sebacic acid, etc.
Examples include polyester resins obtained by polycondensing at least one functional carboxylic acid with at least one glycol such as ethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol, and decamethylene glycol. can. The present invention is particularly effective when polyethylene terephthalate, polyethylene-2゜6-naphthalate, polyethylene-α,β-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate is used as the polyester resin. You can get the same effect. In addition, other types of polymers may be blended or copolymerized with the polyester resin within a range that does not impede the object of the present invention. In addition, the inherent viscosity of the polyester resin used (measured in orthochlorophenol at 25°C) is usually 0. 4 to 2.0, preferably 0.5 to 1.0.

The resin constituting the biaxially stretched film in the present invention includes:
Inorganic or organic additives such as antioxidants, heat stabilizers, lubricants, pigments, and ultraviolet absorbers may be included.

The thickness of the biaxially stretched film in the present invention is not particularly limited, but is usually 0. 1 to 1500 μm, preferably 0.
It is 5 to 300 μm.

In the present invention, a particle size of 0°2 μm is contained in the biaxially stretched film.
It is desirable that the above particles are not included, or even if they are included, the center line average roughness of the surface is 0.02 μm or less, preferably 0.01 μm or less, because the effects of the present invention will be significant.

The slippery film of the present invention has a composite layer mainly composed of organic particles having a shell-core structure and a water-soluble or water-dispersible resin on at least one side of the biaxially stretched film.

The water-soluble or water-dispersible resin used in the present invention may be any resin that can be dissolved or dispersed in water, such as thermoplastic,
Thermosetting properties are not particularly important, but representative examples include acrylic resins, urethane resins, polyester resins, olefin resins, fluorine resins, vinyl resins, chlorine resins,
Examples include styrene resins, various graft resins, epoxy resins, urea resins, silicone resins, and polyamide resins. Among them, particularly suitable water-soluble or water-dispersible resins include the following acrylic resins:
Vinyl resin, urethane resin, polyester resin,
Mention may be made of various graft resins or block polymers or mixtures thereof. However, water solubility or water dispersibility here refers to a slight amount, and although the amount is not particularly limited, it is usually 20% by weight or less, preferably 10% by weight.
Below, substances outside the waterside, such as various organic solvents, may be included.

Specific examples of acrylic resins preferably used as water-soluble or water-dispersible resins in the present invention include at least 40 mol% of acrylic and/or methacrylic monomers and 0.1 to 20 mol% of other functional group-containing monomers. , with about O to 49.9 mole % of one or more halogen-free monoethylenically unsaturated monomers, or at least 25 mole % of acrylic acid, methacrylic acid or alkyl esters of acrylic acid or methacrylic acid. and 1 to 50 mol% of comonomers selected from vinylsulfonic acid, allylsulfonic acid, methacrylsulfonic acid, p-styrenesulfonic acid and salts of these acids. be able to.

Specific examples of vinyl resins preferably used as water-soluble or water-dispersible resins in the present invention include the general formula % (where R1 and R2 are hydrogen or an alkyl group, Ml, M
2 represents hydrogen, alkali metal, alkaline earth metal, ammonium (including substituted ammonium), alkyl group,
Ml and M2 are not both alkyl groups. ) can be mentioned.

Specific examples of urethane resins preferably used as water-soluble or water-dispersible resins in the present invention include polyurethanes whose affinity for water is increased by carboxylic acid groups, sulfonic acid groups, or sulfuric acid half-ester bases. Can be done. However, carboxylic acid groups, sulfonic acid groups,
The amount of base such as sulfuric acid half ester base is 0.5 to 15% by weight.
is preferred, and examples of polyhydroxy compounds used in the synthesis of polyurethane include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,
5-bentanediol, diethylene glycol, triethylene glycol, polycaprolactone, polyhexamethylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylolethane, pentaerythol, Glycerin and the like can be mentioned. Examples of the polyisocyanate compound include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, an adduct of tolylene diisocyanate and trimethylolpropane, an adduct of hexamethylene diisocyanate and trimethylolethane, and the like. Examples of the carboxylic acid-containing polyol include dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid, and trimellitic acid bis(ethylene glycol) ester. Examples of amino acid-containing carboxylic acids include β-aminopropionic acid, γ
-aminobutyric acid, p-aminobenzoic acid and the like. Examples of hydroxyl group-containing carboxylic acids include 3-hydroxypropionic acid, γ-hydroxybutyric acid, p-(2-
Hydroxyethyl)benzoic acid, malic acid, etc. can be mentioned. Examples of compounds having an amino group or a hydroxyl group and a sulfonic group include aminomethanesulfonic acid, 2-
Examples include aminoethanesulfonic acid, 2-amino-5-methylbenzene-2-sulfonic acid, sodium β-hydroxyethanesulfonate, propane sultone and butane sultone addition products of aliphatic diprimary amine compounds, and the like. Preferred examples include propane sultone adducts of aliphatic diprimary amine compounds. Furthermore, examples of compounds containing an amino group or a hydroxyl group and a sulfuric acid half-ester group include aminoethanol sulfuric acid, ethylenediamine ethanol sulfuric acid, aminobutanol sulfuric acid, hydroxyethanol sulfuric acid, γ-hydroxypropanol sulfate, α-hydroxybutanol sulfuric acid, and the like. It will be done.

Or, Special Publication No. 42-24194, Special Publication No. 46-7
No. 720, Special Publication No. 1973-10193, Special Publication No. 49-3
No. 7839, JP-A-50-123197, JP-A-53
Examples thereof include polyurethane resins having an anionic group or polyurethane resins similar thereto, which are known in Japanese Patent Application Laid-open No. 126058, JP-A-54-138098, and the like.

The main components of the polyurethane-forming component are polyisocyanate, polyol, chain extender, crosslinking agent, and the like.

Further, a resin comprising a polyol having a molecular weight of 300 to 20,000, a polyisocyanate, a chain lengthening agent having a reactive hydrogen atom, a group that reacts with an isocyanate group, and a compound having at least one anionic group is preferable.

The anionic group in the polyurethane resin is preferably used as -80H, -0802H, -COOH and their ammonium, lithium, sodium, potassium or magnesium salts.

The amount of anionic groups in the polyurethane resin is 0.05
% to 8% by weight is preferred.

Specific examples of polyester resins preferably used as water-soluble or water-dispersible resins in the present invention include dicarboxylic acids in which 0.5 to 15 mol% of the total dicarboxylic acid components are dicarboxylic acids containing sulfonic acid metal bases; Examples include polyester copolymers comprising alcohols.

However, the above-mentioned sulfonic acid metal base-containing dicarboxylic acids include sulfoterephthalic acid, 5-sulfoisophthalic acid,
4-sulfophthalic acid, 4-sulfonaphthalene-2,7-
Examples include metal salts of dicarboxylic acid, 5[4-sulfophenoxy]isophthalic acid, and particularly preferred are 5-sodium sulfoisophthalic acid and sodium sulfoterephthalic acid.

Alternatively, examples may include those containing an aqueous polyester resin having at least one type of free carboxylic acid group and carboxylic acid group in the molecule, a crosslinking agent having two or more epoxy groups, and, if necessary, a reaction accelerating compound. however,
In order to introduce a carboxylic acid group into the molecule of this aqueous polyester resin, for example, trimellitic anhydride, trimellitic acid, pyromellitic anhydride, pyromellitic acid, trimesic acid, cyclobutanetetracarboxylic acid, dimethylolpropionic acid, etc. It is preferable to use a polyvalent compound as one of the raw materials for producing the polymer. Further, a carboxylic acid salt can be introduced by neutralizing the carboxylic acid group introduced into the polymer with an amino compound, ammonia, an alkali metal, or the like.

Specific examples of various graft resins preferably used as water-soluble or water-dispersible resins in the present invention include comb-shaped graft polymers having a back chain of polymethyl methacrylate and a branch chain of poly 2-hydroxyethyl methacrylate. Can be done.

Another example is an acrylic graft polyester in which the trunk polymer is polyester and the branch polymers are acrylic polymers.

However, the polyester serving as the backbone polymer of this aqueous polyester-acrylic graft polymer is a substantially linear polymer synthesized from a polybasic acid or its ester-forming derivative and a polyol or its ester-forming derivative. Polybasic acid components of this polymer include terephthalic acid, isophthalic acid, lataric acid, phthalic anhydride,
, 6-naltale dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer acid, and the like. Two or more types of these components can be used. Furthermore, in addition to these components, unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid, etc., and hydroxycarboxylic acids such as p-hydroxybenzoic acid, p-(β-hydroxyethoxy)benzoic acid, etc. may be used in small proportions. can. The proportion of the unsaturated polybasic acid component and the hydroxycarboxylic acid component is at most 10 mol%, preferably 5 mol% or less.

In addition, as a polyol component, ethylene glycol, 1
, 4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1.6-
Hexanediol, 1,4 cyclohexane dimetatool, xylylene glycol, dimethylolpropionic acid,
Examples include glycerin, trimethylolpropane, poly(ethylene oxide) glycol, poly(tetramethylene oxide) glycol, and the like. Two or more types of these can be used.

Examples of monomers for the acrylic polymer include alkyl acrylate, alkyl methacrylate (alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group,
-ethylhexyl group, cyclohexyl group, phenyl group,
(benzyl group, phenylethyl group, etc.): Hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate: acrylamide, methacrylamide, N-methylmethacrylamide, N - Amide group-containing monomers such as methylacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N,N-dimethylolacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-phenylacrylamide: N, N - Amino group-containing monomers such as diethylaminoethyl acrylate and N,N-diethylaminoethyl methacrylate; Epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; acrylic acid, methacrylic acid and their salts (sodium salt, potassium salt, ammonium salt) ) and other monomers containing a carboxyl group or a salt thereof. These 5 6 can be used in combination with other types of monomers. Examples of other monomers include epoxy group-containing monomers such as allyl glycidyl ether; monomers containing sulfonic acid groups or their salts such as styrene sulfonic acid, vinyl sulfonic acid, and their salts (sodium salts, potassium salts, ammonium salts, etc.) : Crotonic acid, itaconic acid, maleic acid, fumaric acid and their salts (sodium salt, potassium salt,
Monomers containing carboxyl groups or their salts such as ammonium salts etc. Monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride: Vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl Examples include trisalkoxysilane, alkylmaleic acid monoester, alkylfumaric acid monoester, acrylonitrile, methacrylaterile, alkylitaconic acid monoester, vinylidene chloride, vinyl acetate, vinyl chloride, and the like. The above-mentioned monomers are copolymerized using one type or two or more types.

Specific examples of block polymers preferably used as water-soluble or water-dispersible resins in the present invention include water-based acrylic polymer-polyester block polymers.

However, the monomers of the acrylic polymer constituting this block polymer include, for example, alkyl acrylate,
Alkyl methacrylate (alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group,
(phenylethyl group, etc.): Hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate: acrylamide, methacrylamide, N-methylmethacrylamide, N-methylacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N,N-dimethylol acrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N-
Amide group-containing monomer such as phenylacrylamide: N
, N-diethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, and other amino group-containing monomers; glycidyl acrylate, glycidyl methacrylate, and other epoxy group-containing monomers; acrylic acid, methacrylic acid, and their salts (sodium salts, potassium salts, Monomers containing a carboxyl group or a salt thereof such as ammonium salt, etc.) can be mentioned. These can be used in combination with other types of monomers. Other types of monomers include epoxy group-containing monomers such as allyl glycidyl ether; monomers containing sulfonic acid groups or their salts such as styrene sulfonic acid, vinyl sulfonic acid, and their salts (sodium salts, potassium salts, ammonium salts, etc.); Monomers containing carboxyl groups or salts thereof such as crotonic acid, itaconic acid, maleic acid, fumaric acid and their salts (sodium salt, potassium salt, ammonium salt, etc.): acid anhydrides such as maleic anhydride, itaconic anhydride, etc. Monomers containing: vinyl isocyanate, allyl isocyanate, styrene, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid monoester, acrylonitrile, methacrylate trile, alkyl itaconic acid monoester, vinylidene chloride, vinyl acetate, vinyl chloride, etc. can be mentioned. The above-mentioned monomers can be copolymerized using one type or two or more types, but from the viewpoints of imparting hydrophilicity to the acrylic polymer, dispersion stability of the aqueous solution, adhesion to the polyester film, etc., hydroxyl groups, Those having a functional group such as an amide group, a carboxyl group, or a salt thereof (sodium salt, potassium salt, ammonium salt, etc.) are preferred.

Polyester, which is another component of the aqueous block polymer, is a substantially linear saturated polyester synthesized from a polybasic acid or its ester-forming derivative and a polyol or its ester-forming derivative. The polybasic acid components of this polyester include terephthalic acid,
Examples include isophthalic acid, 9 20 phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer acid, etc. can. Two or more types of these can be used.

In addition, p-hydroxybenzoic acid, p-
Hydroxycarboxylic acids such as (β-hydroxyethoxy)benzoic acid can also be used.

In addition, as a polyol component, ethylene glycol, 1
, 4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-
Examples include hexanediol, 1,4-cyclohexane dimetatool, xylylene glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, poly(ethylene oxide) glycol, poly(tetramethylene oxide) glycol, and the like. These are 2
More than one species can be used.

This polyester is preferably an aqueous polymer; for example, one containing a compound having a hydrophilic group such as an organic sulfonate, a carboxylate, diethylene glycol, polyalkylene ether glycol, etc. is advantageous for making an aqueous dispersion and is therefore preferred. . The introduction of this carboxylic base is
Usually, a trifunctional or more functional carboxylic acid is used, but since the carboxylic acid branches during the polymerization process and tends to gel, it is desirable to keep the copolymerization ratio small. In this respect, introduction of hydrophilic groups using sulfonic acid, diethylene glycol, polyalkylene ether glycol, etc. does not have these problems and is more advantageous.

In order to introduce a sulfonate group into the polyester molecule, for example, 5-Na sulfoisophthalic acid, 5-ammonium sulfoisophthalic acid, 4-Na sulfoisophthalic acid, 4-methylammonium sulfoisophthalic acid, 2-
Na sulfoterephthalic acid, 5-sulfoisophthalic acid,
It is preferable to use sulfoisophthalic acid for 4-, and a sulfonic acid alkali metal salt or sulfonic acid amine salt-based compound such as sulfoterephthalic acid or Na sulfosuccinic acid for 2-. The polyhydric carboxylic acid or polyhydric alcohol having a sulfonate group accounts for 0.0% of the total polyhydric carboxylic acid component or polyhydric alcohol component. 5-20 mol%, even 1-1
Preferably, it accounts for 8 mol%.

Various crosslinking agents may be used in the water-soluble or water-dispersible resin in the present invention, if necessary. The types are not particularly limited, but representative examples include isocyanate crosslinking agents, isocyanurate crosslinking agents, melamine crosslinking agents,
Examples include urea-based crosslinking agents and epoxy-based crosslinking agents.

Specific examples of epoxy crosslinking agents include polyepoxy compounds, jepoxy compounds, monoepoxy compounds, and examples of polyepoxy compounds include sorbitol, polyglycidyl ether, polyglycerol polyglycidyl ether, and pentaerythritol polyglycidyl ether. , diglycerol polyglycidyl ether, triglycidyl tris(2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether,
Examples of trimethylolpropane polyglycidyl ether and jepoxy compounds include neopentyl glycol diglycidyl ether, 1°6-hexanesiol diglycidyl ether, resorcin diglycidyl ether,
Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and monoepoxy compounds include:
Examples include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. In addition, as an isocyanate crosslinking agent,
For example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Examples include xylylene diisocyanate. Examples of the urea-based crosslinking agent include dimethylolurea, dimethylolethyleneurea, dimethylolpropyleneurea, tetramethylolacetyleneurea, 4methoxy5dimethylpropyleneurea dimethylol, and the like. As the melamine-based crosslinking agent, compounds obtained by etherifying a methylolmelamine derivative obtained by condensing melamine and formaldehyde with lower alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc., and mixtures thereof are preferable. As a methylolmelamine derivative,
Examples include monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, and hexamethylolmelamine. These crosslinking agents may be used alone, or in some cases, two or more types may be used in combination.

In the present invention, the thickness (T) of the composite layer is preferably 0.001 μm to 10 μm, more preferably 0.01 μm.
m~1.0μm1 More preferably 0.06μm~0.
It is 4 μm. If the thickness is less than 0.001 μm, it is undesirable because the particles will drop off significantly, and if it is thicker than 10 μm, the adhesion during the rubbing test will deteriorate rapidly, which is not preferred.

The thickness (T) of the composite layer can be measured by various methods, for example, by measuring the cross section of the laminated film with an electron microscope,
If the resin layer can be removed using a solvent or the like, it can also be determined from the difference in level between the removed portion and the unremoved portion.

Another component constituting the composite layer is organic particles having a shell-core structure. Having a shell-core structure means that the particles have a multilayer structure of two or more layers. That is, it refers to a particle in which a spherical organic particle corresponding to a core portion is coated with one or more layers having a specific thickness and having a different chemical structure.

In the present invention, it is preferable that the shell portion (the outermost layer in the case of a multilayer of three or more layers) of the organic particle is more flexible than the core portion because the effects of the present invention will be more pronounced. Further, it is more preferable that the glass transition temperature Tgs of the shell portion is 50° C. or lower and the glass transition temperature Tgc of the core portion is higher than Tgs, from the viewpoint of easy slippage and less scratching.

The resin constituting the core portion of the organic particles is not particularly limited, but examples include various resins such as acrylic resins, styrene resins, imide resins, and amide resins, and copolymer resins thereof. Furthermore, the resin constituting the shell portion is not particularly limited, but examples include acrylic resins such as acrylic rubber, styrene resins such as styrene-butadiene rubber or acrylonitrile styrene rubber, and resins such as copolyamide resins. Among them, rubber-based resins are preferred.

The ratio of the radius of the core portion to the thickness of the shell portion of the organic particles is not particularly limited, but is usually 9.510°5 to 0.5/
It is in the range of 9.5.

The organic particles have an average particle size (D
) is necessary. However, the average particle diameter referred to here is a weight average diameter, and can be determined, for example, by a sedimentation method. If the average particle diameter (D) 7 is smaller than 0.002 μm, it is not preferable because slipperiness is insufficient, whereas if it is larger than 8.0 μm,
This is not preferable because the particles drop significantly.

In the present invention, the ratio (D/T) of the average particle diameter (D) of the organic particles to the thickness (T) of the composite layer is 1. .

When it is in the range of 1 to 80, the slipperiness is further improved and particles do not fall off significantly, which is more preferable.

The amount of the organic particles added in the composite layer is not particularly limited, but is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 3% by weight or less.

In the present invention, it is preferable that the composite layer is stretched. Whether or not the composite layer has been stretched can be determined by evaluating the degree of orientation of the composite layer using a method such as FT-IR. When the composite layer is stretched, the adhesiveness between the resin constituting the composite layer and the biaxially stretched film and the adhesiveness between the resin constituting the composite layer and the organic particles are improved, which is preferred. It is.

Next, a typical method for manufacturing the slippery film of the present invention will be described, but the method is not particularly limited thereto.

After drying the resin raw material (resin that should form the biaxially stretched film) under specified conditions as necessary, using an extruder or other method, the resin raw material is melted and then formed into a film (usually on a cooling drum).
do. A film obtained by stretching the thus obtained unstretched film-like material or unstretched film more than uniaxially as necessary (for example, if the resin is polyethylene terephthalate,
2.0 times to 9.0 times at 5 to 130°C, and 2.0 times to 12.0 times at 100°C to 165°C in the case of polypropylene
After surface treatment such as corona discharge treatment as necessary, a water-soluble or water-dispersible resin is coated on the surface using known methods (gravure coating, reverse coating, kiss coating, die coating, bar code coating, comma coating, etc.). coat, etc.). The composite film thus obtained is further stretched if necessary. The stretching direction is not particularly limited, but when applied onto a film stretched in a uniaxial direction, it is usually stretched in a direction perpendicular to the uniaxial direction. Further, when coating on an unstretched film, it may be stretched in either the longitudinal or lateral directions, or may be stretched in two axial directions at the same time. After stretching in this manner, heat treatment or the like may be performed while relaxing the film, if necessary.

The method of measuring the characteristic value and the method of evaluating the effect of the present invention are as follows.

(1) Slip property Measured according to ASTM D-1894.

(2) A film with a scratch thickness of 250 μm was wound at a winding speed of 80 m/min.
After winding it up for 00 m, the surface was examined for scratches. Those in which the number of scratches did not increase at all during winding were evaluated as "○", and the others were evaluated as "1x".

(3) White spots In order to evaluate scratches in the previous section, aluminum was vapor-deposited on each of the front and back sides of the rolled film, and white spots (referred to as white spots) partially visible due to changes in reflectance due to surface scratches were observed per 200 m2. 1 or less
◎”, “○” for 2 or less, “×” for 3 or more
”.

〔Example〕

Hereinafter, the present invention will be explained in more detail based on examples.

However, the present invention is not limited to the following examples.

Example 1 Pomopolymer chips of polyethylene terephthalate manufactured by a conventional method (intrinsic viscosity: 0.62, melting point = 25
9°C) was dried under reduced pressure (3mmHg) at 180°C for 2 hours. The chips were fed to an extruder equipped with a screw with a compression ratio of 3.8 at 280°C, melted and extruded from a T-shaped nozzle, and then wound around a cooling drum with a surface temperature of 20°C using an electrostatic application method to cool and solidify. It was made into an unstretched film. The obtained unstretched film was stretched in the longitudinal direction by roll stretching at 90°C.
．． The film was stretched 3 times to obtain a -axis stretched film.

Next, a resin emulsion of an equimolar copolymer of acrylic acid methyl ester and acrylic acid butyl ester (however -C
Contains 2゜0 mol% each of H2-OH and -COOH) 100
A coating material containing 4 parts by weight of organic particles B having an average particle size of 0.1 μm was applied to one side of the -axis stretched film using a gravure coating method, and then dried with hot air. The coated film was stretched 3.5 times in the transverse direction at 100°C, and then heat treated at 220°C for 2 seconds while relaxing by 2% in the transverse direction, so that the thickness (T) of the composite layer was 0.05 μm and the film was stretched 3.5 times in the transverse direction. A laminated film having a stretched film layer thickness of 50 μm was obtained. Table 1 shows the results of evaluating the physical properties of the obtained laminated film (slippery film).

However, organic particles B have a core portion made of a copolymer of methyl methacrylate and ethyl methacrylate in a molar ratio of 9:1, and a shell portion made of a copolymer of methyl methacrylate and butyl methacrylate in a molar ratio of 5:5. These are organic particles with a shell-core structure made of a copolymer of

Comparative Example 1 1 2 In Example 1, organic particles B with an average particle size of 0.1 μm were changed to organic particles A with an average particle size of 0.001 μm, and the thickness (T) of the composite layer was changed to 0.0005 μm. The same procedure as in Example 1 was carried out except for the following.

However, the organic particles A are organic particles of methacrylic acid methyl ester pomopolymer.

Comparative Example 2 In Example 1, the average particle diameter of organic particles B was set to 0°01μ.
m and the thickness (T) of the composite layer to 0°0005μ
The same procedure as in Example 1 was carried out except that m was changed.

Example 2 In Example 1, the average particle size of organic particles B was set to 0°6 μm.
Example 1 was carried out in the same manner as in Example 1, except that the thickness (T) of the composite layer was changed to 0°3 μm.

Example 3 In Example 1, the average particle size of organic particles B was set to 2°0 μm.
Example 1 was carried out in the same manner as in Example 1, except that the thickness (T) of the composite layer was changed to 1 to 90 μm.

Example 4 In Example 1, the average particle size of organic particles B was set to 6°0 μm.
Example 1 was carried out in the same manner as in Example 1, except that the thickness (T) of the composite layer was changed to 3°0 μm.

Comparative Example 3 The same procedure as in Example 1 was carried out except that the average particle size of organic particles B was changed to 10 μm and the thickness (T) of the composite layer was changed to 5°0 μm.

Comparative Example 4 In Example 1, organic particles B with an average particle size of 0.1 μm were changed to organic particles A with an average particle size of 0.6 μm, and the thickness (T) of the composite layer was changed to 0.1 μm. The same procedure as in Example 1 was carried out except that the thickness was changed to 3 μm.

Example 5 In Example 1, the average particle size of organic particles B was set to 0°6 μm.
Example 1 was carried out in the same manner as in Example 1, except that the thickness (T) of the composite layer was changed to 0.03 μm.

Example 6 In Example 1, the average particle diameter of organic particles B was set to 2°0 μm.
Example 1 was carried out in the same manner as in Example 1, except that the thickness (T) of the composite layer was changed to 0.02 μm.

Example 7 Example 1 except that the organic particles B with an average particle size of 0.1 μm were changed to organic particles C with an average particle size of 0.6 μm, and the thickness (T) of the composite layer was changed to 0.3 μm. is Example 1
It was carried out in the same way.

However, in organic particles C, the core part is made of a copolymer of methyl methacrylate and ethyl methacrylate in a molar ratio of 9:1, and the shell part is made of a copolymer of methyl methacrylate and butyl acrylate in a molar ratio of 4:6. These are organic particles with a shell-core structure made of a copolymer of

Example 8 In Example 2, the amount of organic particles B added was 105 Except for changing to weight%. did.

6 Implemented in the same manner as in Example 2 [Effects of the Invention] The present invention uses particles having a shell-core structure, so scratches and white spots are significantly reduced without impairing the sliding properties, and the surface condition is improved. A good film could be obtained.

Claims (5)

[Claims] (1) A composite layer containing organic particles having a shell-core structure with an average particle size of 0.002 to 8.0 μm and a water-soluble or water-dispersible resin as main components was provided on at least one side of the biaxially stretched film. An easily slippery film characterized by: (2) Average particle diameter (D) of the organic particles and thickness of the composite layer (
The slippery film according to claim 1, wherein the ratio (D/T) of T) is in the range of 1.1 to 80. (3) The slippery film according to claim 1, wherein the composite layer is stretched. (4) The slippery film according to claim 1, wherein the shell portion of the organic particles is more flexible than the core portion. (5) Glass transition temperature Tgs of the shell portion of the organic particles
is 50°C or less, and the glass transition temperature Tg of the core portion is
The slippery film according to claim 1, wherein c is higher than Tgs.