JPH0327935A - Film laminate - Google Patents

Abstract

PURPOSE:To enable a resin film having a highly fluorinated surface to be obtained in a short time by providing a specific surface layer on a thermoplastic resin film surface, after that, plasma-processing it under fluorine gas. CONSTITUTION:The A layer surface of a thermoplastic resin laminated film consisting of at least A, B layers is discharge-processed under the existence of fluorine gas, and made to satisfy formulas, I, II. In the formulas I, II, gamman/A shows the polar force component (erg/cm<2>) in entire surface energy of the A layer surface prior to the discharge process, gamman/AF shows the entire surface energy (erg/cm<2>) of the A layer surface after the discharge process, and gammaB shows the entire surface energy (erg/cm<2>) of the B layer surface. For instance, on one side of polyester, the resin being 10erg/cm<2> or less in its polar force component of the entire surface energy is laminated, and the A layer surface is plasma-processed under the existence of fluorine gas. Thus, a film laminated matter being cheap and having processing aptitude can be obtained, wherein it has a fluorine contained polymeric film with excellent durability in one side and also has easy adhesiveness in the other side.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Application of the Invention) The present invention provides a coating of a fluorine-containing polymer compound having excellent durability, one of which is f1-1, and one of which is b-contact.
It concerns a collection of film that is sexually charged and has a female value.

(Conventional technology) Heat + of polyester, polyamide, polypropylene, etc.
1J plastic resin films, especially polyester films such as polyethylene terephthalate, have excellent mechanical strength, dimensional stability, transparency, heat resistance, and chemical resistance, and are used as base films for magnetic tapes, insulating tapes, photographic films, tracing films, Widely used in applications such as food packaging films.

However, these thermoplastic RT resin films usually have water repellency, stain resistance, anti-fog properties, abrasion resistance, P16 weather resistance,
It lacks water resistance, moisture absorption resistance, bleat-out resistance, blocking resistance, etc.

Conventionally, in order to compensate for these drawbacks, for example, polytetrafluoroethylene, polyvinyl fluoride, boron-fluorinated vinylidene, perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer, tetrafluoroethylene hexafluoropropylene copolymer were used. Fluorinated films such as ethylene-tetrafluoroethylene copolymer, polyfluorotrifluoroethylene, etc. are used, but these films are extremely commercially priced and are usually used in a laminated state. In order to make these surfaces easily adhesive in one minute, the disadvantage of requiring dangerous chemical treatments and resulting in historically high costs is eliminated.

・There is a method of coating thermoplastic resin films such as polyester films with fluororesin, etc., but increasing water repellency lowers the adhesion to the base material, and increasing adhesion lowers water repellency. It has the following drawbacks.

Plasma treatment with fluorine gas in history! There is a force method to modify the surface of polyester film, but it requires a long time to impart properties similar to polytetrafluoroethylene to polyester film, making it expensive and having the disadvantages that there are few applications for which it can be used. I'm angry.

Also, when manufacturing polyester films etc., do we blend fluorine-based low molecules or polymers? There is a method, but the drawback is that if you blend enough amount to achieve water repellency of 1/1 mm, the T/L of the base film mouth will be low.

(Intermediate Points to be Solved by the Invention) The present invention attempts to solve the following problems, and therefore, it does not damage the external properties of the base film, and one side has a highly durable film, and is coated with a It is an object of the present invention to obtain a film laminate having a high-density-R coating, LL coating, which has easy adhesion, is inexpensive, and has good adhesion properties.

(Means for Solving the Problems) In view of the above-mentioned circumstances, the Ministry of the Invention and others conducted intensive research and arrived at the present invention.

That is, the present invention provides a thermoplastic resin laminated film consisting of at least A1B layers, the surface of the A layer being subjected to discharge treatment in the presence of fluorine gas, and satisfying the following general formula: lI:. It is a resin waste film.

γ father≦10 γAP−γ■≦−20 [Here, γ father is discharge treatment 11! Full surface rf of previous A layer surface
1j Extreme force component in ergy (erg/cJ)
, γ is the total surface energy of the A layer surface immediately after discharge treatment (
erg/cril), γ,, is the entire table of Bfl table city 1 +
fii x energy (erg/clTl)] In detail, for example, a resin whose polar force component in the total surface energy is 10 erg/c+fl or more is laminated on one side of polyester, and the surface of layer A is treated with fluorine gas. By plasma treatment in the presence of polyester, the total surface energy of layer A is reduced, and the difference from the total surface energy of layer B, that is, polyester, is -20 erg/cI1! This is a laminated film consisting of a fluorinated A-layer surface with high hydrophobicity and a B-layer surface made of polyester with good adhesiveness.

The laminated film is a film that has the ease of handling of a polyester film, and on the other hand, has hydrophobicity comparable to that of a fluorine film.

Furthermore, 11R, which is coated with a resin on the BN surface on the opposite side of the A-layer surface, has higher mechanical energy than polyester and has better blue engraving and printability than polyester, creating a film with high added value. It can be done.

In the present invention, methods for laminating layer A include extrusion method, extrusion lamination method, dry lamination method, and coating method, and coating methods include offline coating method and inline coating method, as described above. In-line coating method is preferred from the viewpoint of adhesion.

More specifically, it is preferable that the B layer is a film laminate that has undergone oriented crystallization, and that the A layer is laminated before the oriented crystallization of the B layer is completed.

The method of providing an easily adhesive layer in the present invention is no different from the method of providing an easily fluorinated surface, and there is no need to provide it.

Therefore, the most suitable embodiment is a method in which the A layer and the adhesive layer are simultaneously provided and then the surface of the A layer is subjected to discharge treatment under fluorine gas, but the method is not limited thereto. For example, it is assumed that many combinations will be required, such as sequentially providing the A layer and the easy-to-contact h'J, and performing fluorine discharge treatment in between.
It may be selected as appropriate depending on the purpose.

The resin that can be used in layer A in the present invention is not particularly limited as long as the polar force component in the total surface energy is 10 erg/cJ or less, but examples include the following. Polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate, ethylene-ethyl acrylate, ethylene-ethyl acrylate, ethylene-ethyl acrylate, Ethylene polymers such as ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, maleic anhydride grafted polyethylene, ethylene-vinyl alcohol co-adhesive polymer, propylene polymer such as polypropylene, chlorinated polypropylene, polybutadiene, polyisobrene, Styrene-butanoene copolymer, acrylic-tolyl, butadiene copolymer (
Polymers, rubber resins such as polychloroprene, ethylene-propylene copolymers, etc.

In addition, as a resin for directing VJ contact M+, etc., which is stacked on the 1st floor opposite to the A layer surface, polyhydric alcohols such as ethylene glycol and bentaerythritol are used. Vinyl resins such as polyvinyl acetate, polyvinyl chloride, vinylidene borylate and their polymers; acrylic acid, methyl methacrylate, hydroxy/methyl acrylate, styrene, glycinol methacrylate, methyl acrylate,
Acrylic resins prepared using ethyl acrylate, etc.; Acrylic resins prepared using isophthalic acid, adipic acid, sebacic acid, ethylene glycol, diethylene glycol, neopentylene glycol, polyethylene glycol, polytetramethylene glycol, etc. polyester resin; and g. Polyurethane resins prepared from mud glycol deposits and diisocyanates, polyamide resins such as nylon 6 and methoxymethylated nylon 6, carbonate resins such as polycarbonate and polyester polycarbonate, and alkylol or alkoxyalkyl groups with f-1 Urea-based, ethylene W
Materials such as base resins and melamine resins can be used. For example, the density between these laminated resins and layer B is li+
There is no problem in using additives exclusively for crosslinking agents in order to achieve Jt=. The following resins L can be used for the A layer if they satisfy the above formula.

The thermoplastic resin film (base film) on which the L resin is laminated includes polyester film, polyamide film, polycarbonate film, polyphenylene sulfide film, polyetherimide film,
Examples include polyether sulfone film, polyolefin film, cellulose film, PVA film, acrylic film, and vinyl chloride film. The material is selected.

The most commonly used materials include polyester film, polyamide film, polycarbonate film, and cellulose film.

The base film listed in L is its material, 44 794
It is usually obtained by melting and filling the resin, or by dissolving the resin in a solvent and casting the resin. Such unstretched films can be processed as needed.
After axial or biaxial stretching, the composition No. 11 is attached to the surface by the method described below.The composition is applied to the unstretched or uniaxially stretched base film.
'． A method of further stretching, if necessary, is more preferable from the viewpoints of adhesion between the base film and the composition, ease of slipping, and durability of the obtained film.

Historically, the thickness of the above-mentioned resin is at least 0.01 μm, and if the thickness is less than that, it is difficult to obtain the effect of the discharge treatment under fluorine gas.

Discharge treatment in the present invention includes glow discharge, corona discharge,
Although arc discharge is present, plasma treatment with glow discharge is preferred.

The fluorine gas used in the present invention has a carbon number of 1
~15 il'J: a rust-like, split-like, cyclic alkane alkene substituted with 1 to 14 fluorine atoms, preferably 1/2 to 12 hydrogen atoms are fluorine atoms, and 1 value is substituted with fluorine atoms. It is a compound in which the hydrogen in the - part is replaced with boron, boron, or chlorine. CF4 as a 54-like compound
,C2F4,C. , F. , C2 H2F, C2 HF:
+ + C2 c QF: + + CF2”CH2 .
C:] FN + C4 F I+1+ C++ F
141CB rF:l+ Cc (!.2 F2 +
Cc Q:+F+CHF3. C2F. , etc. Each of these can be used in combination of one or two or more persimmons.

In the present invention, a laminated thermoplastic resin film is placed in the above-mentioned fluorine gas atmosphere, and glow discharge is performed, for example. There are no particular restrictions on the flow rate of fluorine gas, but it is usually about 0.0% with respect to the volume IQ of the discharge area. 05~30S
It is preferable to set it as TPcril/min.

It is also possible to mix an inert gas in the glow discharge area.
T: I mean it. Glow discharge can be performed according to a known method, for example at -20 to 100°C, preferably from O to 50'C.
temperature, 0.0 1 to 3 Torrs preferably 0
．． 5 ~2. OTo r r atmosphere 2 per ZlQ
0.1-100MH with discharge Iu power of ~l O O w
It is foolish to place it in the H:b' frequency electric field of z.

Satisfy the conditions mentioned above! 1 'By, extremely short I
It is possible to obtain a resin film that exhibits a low surface bending energy between + and ``f.Specifically, it normally requires plasma treatment with fluorine gas F for 30 seconds or more, but according to the present invention, For example, sufficient surface fluorination can be achieved even with plasma treatment for 30 seconds or less, extremely low metaphysical energy can be obtained, and manufacturing can be done at low cost.

In order to take advantage of these advantages, an air-to-air continuous running type discharge treatment method is preferable to a batch type discharge treatment method. The key point in this method is to form an easily fluorinated surface on the resin film in advance (lE). The combination of this surface design and the discharge treatment pit makes it possible for the first time to obtain a resin film that has a highly fluorinated surface with a short discharge treatment.

Next, the present invention will be explained using actual cell examples and comparative examples. In addition, in the following, surface energy, water resistance, waterproof? r: Antifogging properties were measured by the following method.

1. From the contact angle of surface energy water and methylene iodide, D. K. OI'l
ENS. method (J. Appl. Polym. Scl
．． ．． VoLI3 PP 174 1 -1747 (19
69)), the extreme force component and dispersion force component of the physical energy were calculated by 1;l. The total surface energy is expressed as the sum of these.

2 Water-resistant resin film is immersed in water for 7 to 115 minutes, then 90 to 10
It was dried at 0''C for 30 minutes and the surface energy was calculated.

3. 3 with 1 cc of B weight 7'll+ applied to IFi-proof resin film L
After 0 minutes, wipe off the excess B heavy hl+ and check the degree of dirt with JI.
Judgment was made using gray scale for S'/'j s.

4. A beaker half filled with antifogging water was sealed so that the inner surface of the beaker was heated at 35°C for 24U. After leaving it for a period of time, the condition was determined.

A Not cloudy at all B Partially cloudy C Completely cloudy 5. The immediately transferable treated and non-treated surfaces were superimposed, and a film 1-. Apply 5 kg of right weight to 40”C
, Non-treatment Fl after being left at 90%RH for 72 hours! iT+i
The water Y ink was printed and its appearance was evaluated.

Example 1 60 mol% ethylene, 38 mol% methyl methacrylate
, 10 parts of a copolymer consisting of 2 mol% of hydroxyethyl acrylate, 10 parts of a reaction product of trimethylohapropane and tolylene diisocyanate (1:1), 500 parts of toluene, 300 parts of xylene, 1 part of N-methylpyrrolidone.
0 0? A coating solution was prepared by dissolving it in A<.

Separately, polyethylene terephthalate was heated to 280~300″C.
Melt extrusion was carried out at 15°C and cooled with a cooling roll at 15°C. An unstretched film with a diameter of 500 ttm was obtained, and this stretched film L was stretched 3.3 times in the longitudinal direction through a pair of rolls at different circumferential speeds of 85°C.

Coat 1 and 2 liquids of -L on the surface of this film using an air knife method, dry with hot air at 70°C, and prepare resin composition J+=1.
was defeated.

This film was stretched 3.3 times in the transverse direction at 98°C using a teletor, and further heated to a temperature of 200-210°C to a thickness of 50 μm.
Biaxial stretching of (ethylene copolymer layer 0.11 μm),
I got a counterfeit film.

Using this film, CF4 was used at a gas pressure of 1. OTo
r r11f'5 frequency output 1 0 kW % processing pli
Plasma treatment was performed at a speed of 10 m/min (plasma irradiation time: 1 second).

The properties of the resulting film are shown in Table 1.

Practical Example 2 A film was obtained in the same manner as in Example 1 except that the ethylene copolymer was replaced with polystyrene.

Example 3 The same procedure as Example 1 was carried out in Example 1 except that two stretched films were coated.

Comparative Example 1 In Example 1, a polyester film was subjected to plasma treatment in the same manner as in Practical Example 1, except that the lamination treatment was not performed.

Comparative Example 2 In Cell Example 1, polyethylene glycol (molecular ffl4000
) 2 mol%, terephthalic acid 30 mol%, isophthalic acid 6
The same procedure as in Example 1 was carried out except that a copolymer polyester consisting of 8 mol% of hyethylene glycol, 80 mol% of diethylene glycol, and 20 mol% of diethylene glycol was used.

Comparative Example 3 The same procedure as in Example 1 was carried out except that the coating liquid in Practical Example 1 was replaced with a commercially available fluorine-based polymer (tetrafluoroethylene-based) emulsion, and the plasma treatment was not performed.

From Table 1, the non-laminated film (Comparative Example 1), fluorine plasma treatment fI}! The rod force component of the previous surface energy is 1 0
erg/cra or higher (Comparative Example 2) and Teflon-based emulsion coated film (L-1 Example 3) cannot fully satisfy the various characteristics defined in the present invention.
All of the methods of the present invention produce a satisfactory ゜1f.

(Effects of the Invention) The laminated resin film of the present invention has a highly fluorinated surface in a very short time by providing a specific surface layer on the surface of the thermoplastic resin film and then subjecting it to Sg plasma treatment under fluorine gas. Resin film can be obtained.

Claims (1)

[Claims] (1) A thermoplastic resin laminate film comprising at least layers A and B, the surface of the A layer being subjected to discharge treatment in the presence of fluorine gas, and satisfying the following general formula. γ^n_A≦10 γ_A_F−γ_B≦−20 [Here, γ_A is the polar force component (erg/cm^2) in the total surface energy of the A layer surface before discharge treatment, γ_A_
F is the total surface energy (erg
/cm^2), γ_B is the total surface energy of the B layer surface (
erg/cm^2)]