JPH02270549A - Laminate film of thermoplastic resin - Google Patents

Abstract

PURPOSE:To obtain the above film which is good in adhesion and has easy slidableness by laminating composition which consists of at least one kind of water-soluble resin, water-emulsible resin and water-dispersible resin, a specified organic boron high molecular compd. and/or the composite body of the organic boron high molecular compd. and a vinyl alcohol-based polymer as a main component on a thermoplastic resin film. CONSTITUTION:A laminate film of thermoplastic resin is obtained by laminating composition which consists of at least one kind of water-soluble resin, water- emulsible resin and water-dispersible resin, an organic boron high molecular compd. shown in a formular (I) and/or the composite body of the organic boron high molecular compd. and a vinyl alcohol-based polymer as a main component at least on the single side of a thermoplastic film. As the vinyl alcohol-based polymer forming the composite body together with the organic boron high molecular compd., PVA is utilized which is obtained from polyvinyl acetate and has 70 - 100mol.% degree of saponification and 100 - 3,000 degree of polymerization. This laminate film of thermoplastic resin is excellent in adhesive property to every one of a hydrophilic polymer, a hydrophobic polymer and inorganic substances and slidableness is made extremely excellent.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a thermoplastic resin laminated film that is easily slippery and has excellent adhesive properties, particularly adhesive to hydrophilic polymers, hydrophobic polymers, and inorganic materials. This invention relates to a thermoplastic resin laminated film with good quality.

(Conventional technology).

Thermoplastic resin films such as polyester, polyamide, and polypropylene (especially polyester films such as polyethylene terephthalate) have excellent mechanical strength, heat resistance, chemical resistance, transparency, and dimensional stability, and are used as base films for magnetic tapes, It is widely used in applications such as insulating tape, photographic film, tracing film, and food packaging film. However, these thermoplastic resin films usually lack adhesion to hydrophilic polymers, hydrophobic polymers, and inorganic substances. Therefore, when a magnetic material, a photosensitive agent, a matting agent, etc. are to be laminated on this film, it is necessary to apply a corona discharge treatment to the film surface and then provide an anchor coat layer. Furthermore, even if this film is used as a food packaging film and a printed layer or a heat-sealing layer is provided, the adhesiveness between these layers and the thermoplastic resin film is weak, and the heat-sealing strength may be low.

In order to improve the adhesion of thermoplastic resin films, in addition to corona discharge treatment, ultraviolet irradiation treatment,
Methods of performing physical treatments such as plasma discharge treatment, flame treatment, and corona discharge treatment under a nitrogen atmosphere have been proposed. Chemical treatment methods such as alkali treatment and primer treatment, as well as the combination of these and physical treatment methods, are also used.

However, none of these methods can sufficiently improve the adhesion of thermoplastic resin films. In particular, the adhesion between the hydrophilic polymer or hydrophobic polymer and the film is insufficient. Furthermore, among the -1-name type treatments, when primer treatment is performed in particular, the slipperiness of the resulting film generally decreases, resulting in poor workability such as winding performance.

(Problems to be Solved by the Invention) The present invention solves the problems of the conventional art, and its purpose is to provide a material that has good adhesion to both hydrophilic polymers, hydrophobic polymers, and inorganic materials. The object of the present invention is to provide a thermoplastic resin laminated film that is easy to slip.

(Means for Solving the Problems) The present invention provides at least one of a water-soluble resin, a water-emulsifiable resin, and a water-dispersible resin on the surface of a thermoplastic resin film.
By laminating a composition containing a specific organoboron polymer compound and/or a composite of the organoboron polymer compound and a vinyl alcohol polymer as the L component,
This invention was completed based on the inventor's knowledge that the adhesion between a hydrophilic polymer, a hydrophobic polymer, or an inorganic substance and a thermoplastic resin film can be significantly improved, and the film also has excellent slipperiness.

The thermoplastic resin laminated film of the present invention has a small amount of thermoplastic resin film (on both sides, at least one of a water-soluble resin, a water-emulsifiable resin, and a water-dispersible resin) and an organic boron polymer represented by the following formula (I). A thermoplastic resin laminated film in which a composition containing a molecular compound and/or a composite of the organoboron polymer compound (I) and a vinyl alcohol polymer as a main component is laminated, thereby achieving the above-mentioned purpose. Achieved: where p is 10-10000; Q is 0 or l; when q is 1, A is -(X), -(Y)--(Z).

-, X and Z are oxygen-containing hydrocarbon groups having one terminal ether residue and a total number of carbon atoms of 100 or less, and 91m and n are each independently O or 1
It is.

The organic boron polymer compound (1) forming the above-mentioned composite used in the thermoplastic resin laminate film of the present invention can be prepared by the following method.

(1) The following compound (II) having two catechol residues at the end of the molecule is reacted with boric acid, boric acid triester or boric anhydride: where q is O or 1; When 1, A is −(X)ρ −(Y),
-(Z). -, X and Z are oxygen-containing hydrocarbon groups having one terminal ether residue and a total number of carbon atoms of 100 or less, and 91m and n are each independently 0 or 1.

As the boric acid triester described in 1-, an ester of boric acid and a lower alcohol having 4 or more carbon atoms is used. With respect to 1 mole of compound (■), boric acid and boric acid triester are reacted in a proportion of 1 mole, and boric anhydride is reacted in a proportion of 0.5 mole.

(2) A polyetherification reaction is carried out by adding ethylene oxide or the like to di(catechol)borate or a diol containing a di(catechol)borate residue in the molecule and having a total number of carbon atoms of 206 or more. Alternatively, for a diol having a di(catechol)borate or Jt di(catechol)borate residue, a carbon number of 3 to 36
dicarboxylic acid; lower alcohol with 4 or more carbon atoms and 1'
, an ester with the dicarboxylic acid; a halide of the dicarboxylic acid; or a diisocyanate having 4 to 15 carbon atoms.

In the preparation methods described in L (1) and (2), two or more types of raw materials may be used as a mixture. For example, l-(n
In the compound of the formula ), two or more compounds represented by -(A) and - may be used in combination.

Examples of the boron polymer compounds obtained in this way include the following compounds: Xl = 5-100 P1 = 1-100 P2: 5-5000 P3 = 100-10000 xa = 5N100 x, = 1~50 Zl: 1~5゜z2 = 5~100 P5: 5~500 x6 = 10~1000 P6: 3~1000 X7 +z3: 10G, Pg: 1~
1001-1 The vinyl alcohol polymer that forms a composite with the organic boron polymer compound (I) is polyvinyl acetate. ) PVA having a degree of saponification of 70 to 100 mol % and a degree of polymerization of 100 to 3,000 is used. When PVA is used, the degree of saponification is preferably 85 mol % or more -Ll, and the degree of polymerization is preferably 200 or more. A complex of organoboron polymer compound (I) and PVA is formed by mixing the two in a solution or suspension state and heating as necessary. At this time, the mixing ratio of organic boron polymer compound (I) and PVA is 5295 to 95 by weight.
:5, preferably 10:90 to 50:50.

Specifically, for example, a PVA aqueous solution is prepared, and the organic boron polymer compound (I) is added dropwise to the solution while stirring. The reaction temperature at this time is 20 to 100°C, preferably 50 to 80°C. Although the detailed structure of the formed complex is unknown, it is thought to have a structure in which, for example, PVA chains are crosslinked with an organic boron polymer compound.

Among the resins contained in the composition used for the film of the present invention, any of natural polymer compounds, synthetic polymer compounds, and synthetic polymer compounds can be used as the water-soluble resin. Examples of natural polymer compounds include starches,
Contains sodium alginate and proteins (gelatin, etc.). Examples of semi-synthetic polymer compounds include cellulose resins such as carboxycellulose, and starch resins such as soluble starch. Examples of synthetic polymer compounds include poly(meth)acrylates, poly(meth)acrylate-containing copolymers, polyethylene oxide, and modified products of the polymers listed in t. Furthermore, synthetic polymer compounds include epoxy resins prepared using polyhydric alcohols such as ethylene glycol and pentaerythritol; Examples include polyester resins, polyester resins, polyurethane resins, and polyamide resins.

Materials for water-emulsifiable resins and water-dispersible resins include polybutadiene, poly(styrene-butadiene), poly(styrene-butadiene), and poly(styrene-butadiene).
Rubber resins such as (acrylonitrile-butadiene); Vinyl resins such as polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride and their copolymers; acrylic acid, methyl methacrylate, hydroxymethyl acrylate,
Acrylic resins prepared using styrene, glycidyl methacrylate, methyl acrylate, ethyl acrylate, etc.; isophthalic acid, adipic acid, cepatic acid,
Examples include polyamide resins prepared using ethylene glycol, diethylene glycol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, etc.; and polyurethane resins prepared using 4-glycols and diisocyanates.

In addition to the above, water emulsifying resins and water dispersible resins have hydrophilic groups in their molecules, so they exhibit dispersibility in aqueous solvents, or they contain dispersion aids in order to have hydrophilic groups in their molecules. Includes polymer compounds that exhibit dispersibility in aqueous solvents when added a little. ] - Examples of the parenteral group include a phosphonic acid group, a phosphinic acid group, a sulfonic acid group, an ammonium group, and a carboxyl group. Examples of resins containing such hydrophilic groups include polyester, polyurethane, polyamide, acrylic resin,
Examples include epoxy resins and polyolefin resins.

1.Water Distribution Emulsifying resins or water-dispersible resins are conveniently prepared, for example, by an emulsion-type method in which monomers are polymerized in an emulsified state. Of course, it is also possible to prepare the composition using other conventional methods, and in the case of a composition, the obtained polymer can be dispersed in an emulsified state in water using a surfactant or a solvent to form the film described below. It can be conveniently used for preparation.

The resin composition used in the present invention has a low content of -1- mud water-soluble resin, water-emulsifiable resin, and water-dispersible resin (these are collectively referred to as aqueous resin). The molecular compound (I) and the abdominal polymer with the vinyl alcohol polymer are used as the 1: component.The content ratio of the aqueous resin and the composite described in 1-1 is 9515 to 5/95 (w/w),
Preferably it is 80/20 to 20/80 (w/w).

When the aqueous resin exceeds 5% by weight, the adhesion between the resulting film and the hydrophobic polymer is somewhat poor. On the other hand, the complex is 5
If the weight percentage is too large, the adhesion between the resulting film and the hydrophilic polymer will be somewhat poor. The composition may further contain a coloring agent, an antistatic agent, a crosslinking agent, an anti-blocking agent, a lubricant using particles of inorganic or organic materials, other polymers, an ultraviolet absorber, and a deterioration preventive agent, as necessary. A d-agent or the like may be contained in a proportion that does not impair the properties of the resulting film.

■-The thermoplastic resin film (base film) on which the composition is laminated includes polyester film, polyamide film, polycarbonate film, polyphenylene sulfide film, polyetherimide film, polyether sulfone film, polyolefin film, and cellulose film. , PVA film,
Examples include acrylic films and vinyl chloride films, and the optimal material is selected depending on the intended use and required characteristics of the final laminated film. The most commonly used are polyester film, polyamide film, polycarbonate film, cellulose film, etc.

The base film described in 1- above is usually obtained by melting and extruding the thermoplastic resin that is its raw material, or by dissolving the resin in a solvent and casting it. After such an unstretched film is biaxially stretched or 7-axis stretched as required, the composition E is applied (coated) to the surface thereof by the method described below. The method of applying a composition to an unstretched or single-stretched base film and further stretching it as necessary improves the adhesion between the base film and the composition, imparts slipperiness, and improves the durability of the resulting film. It is more preferable from the following points. In the two-wheel stretched base film, the film 111 is wide and the base film L
In order to apply a thin layer of the composition to the film, it is necessary to increase the running speed of the film, making it somewhat difficult to apply the composition evenly.

The thermoplastic resin laminate film of the present invention is prepared, for example, by the following method. First, the composition described in 1- is dissolved, dispersed, or emulsified in water or an aqueous solvent. this is,
For example, a method of adding a complex of a 1° molecular compound, a 1° h molecular compound, and polyvinyl alcohol to latex; a method of adding water or an aqueous solvent while kneading the resin and the complex in a molten state; It can be done. The water distribution solvent is, for example, a solvent containing, in addition to water, a solvent such as an alcohol (for example, methyl alcohol, ethyl alcohol, isopropyl alcohol) in a proportion of 50 weight % or more. (1) The organic solvent is added for the purpose of improving the coating properties of the intermediate base film containing the composition. . i 1 degree mechanical solvent content ii 1 is 50 cities I
What if it is less than 11%? There is no risk of FT-Ki igniting or exploding. For the purpose of improving coating properties, it is also recommended that the composition contain additives such as fluororesins, silicone resins, surfactants, and the like. A coating containing this composition is applied to the surface of the base film described in 1-1, usually from 0.003 to 5 g/d, preferably at 0.01 g/d.
It is dumped at a rate of ~3 g/j. If it exceeds 0.003g//, the adhesiveness between the obtained film and other resin for adhesion will be poor, and if it exceeds 5g/♂ by 1, the slipperiness and blocking resistance of the obtained film will deteriorate. inferior to sex.

! °, Prepare 1 [in the description and apply it to the base film.
In addition to the coating method, for example, a coextrusion coating method, an extrusion lamination method, a dry lamination method, a true melt adhesive method, etc. are also employed.

It is also possible to perform corona discharge treatment or ultraviolet irradiation treatment on the surface of the base film in air or nitrogen atmosphere before or after lamination using the H method such as coating the resin composition described above. . By performing these treatments, the adhesion between the base film and the resin composition layer or the adhesion between the rolled film and other resins is further improved.

The composition used for the film of the present invention contains an fT organoboron polymer compound having a specific structure and/or a composite of the organoboron polymer compound and a vinyl alcohol polymer, an aqueous resin, and an aqueous resin. Since the composition contains 1,
It has good adhesion to hydrophobic polymers, hydrophilic polymers, and inorganic materials. Therefore, the heat+jl plastic resin laminate film of the present invention provided with this resin composition layer is as follows:
Shows good adhesion to both hydrophobic and hydrophilic polymers. Furthermore, the resin composition film containing the composite described in 1- above and the aqueous resin has fine irregularities formed on its surface. Therefore, the film of the present invention also has good slip properties.

(Example) Examples of the present invention will be described below.

Example 1 (1) Preparation of thermoplastic resin laminate film The dicarboxylic acid tP1 position is composed of 50 mol% of terephthalic acid, 47.5 mol% of isophthalic acid and 2.5 mol% of 5-sodium sulfoisophthalic acid, and glycol A sulfonic acid-modified polyester consisting of 50 mol% of ethylene glycol and 50 mol% of neopentyl glycol was synthesized. This polyester is dispersed in water at a ratio of to% by weight, and an organic boron polymer compound (I) is added to the polyester.
-1 (P, = 80) to the polyester 50 tons 1
d% to prepare a coating liquid.

Separately, polyethylene terephthalate was heated to 280 to 300℃.
Melt and extrude at
An unstretched film of 0 μm was obtained, and the unstretched film was passed through a pair of rolls at different circumferential speeds at 90° C. in the longitudinal direction for 3
．． He rose three times.

The surface of this film was coated with the liquid in 1- by gravure coating method (Q+) and dried with hot air at 65° C. to form a resin composition layer. This film was heated horizontally at 98℃ using a tenter.
The film was stretched 3.3 times in the direction of the film and further heat-set at 215° C. to obtain a −axially stretched coated polyester film having a thickness of 50 μm (resin composition layer 0.15 μm).

■ Evaluation of thermal III plastic resin laminated film lO% water dissolution of polyvinyl alcohol (PVA, a/l po IJ?-) and polyvinyl chloride (PVC1 hydrophobic polymer)
A MF (methylformamide) solution was prepared. Each solution was colored with red dye, and the heat I obtained in section (1) was
Printing was carried out separately on the resin composition layer side of two II plastic resin laminated films so that each had a coating weight of 1' and a fit of 2 g//.

Using a cutter knife, cut 41 layers at intervals of 1 on the resulting printing layer.
-1-shaped incisions were made to form 100 squares [I].

Cellophane tape (L pack, Nichiban Co., Ltd. 12) was uniformly applied to each printed area of this thermoplastic resin laminated film, and then the tape was quickly peeled off in a 180 degree direction. After repeating the peel test three times, the number of remaining squares was counted during printing.

The results obtained are shown in Table 1.

The following describes the connections in Examples 2 to 5 and Comparative Examples 1 to 2, which will be described later. ″
The sex and monovalence were also conducted using the same method as the unfruitful color example z1.

Examples 2 to 3 A1 The same as Example 1 except that the type of boron polymer compound was changed as shown in Table 1. Heat obtained + i)
Table 1 shows the results of adhesive evaluation of the plastic resin laminated film. The results of Comparative Examples 1 and 2, which will be described later, are also shown in Table 1.

Comparative Example 1 T'p containing polyester and organoboron polymer compound
[Similar to Example 1 except that the liquid was not coated.]

Comparative Example 2 I1 The same as Example 1 except that the boron polymer compound was not used.

From Table 1, it is clear that the thermoplastic resin laminate film of the present invention exhibits good adhesion to both PVA, which is a hydrophilic resin, and PVC, which is a hydrophobic resin.

It can be seen that the film containing the organic boron polymer compound in the resin composition (Comparative Example 2) has poor adhesion to the hydrophilic resin.

Example 4 A 10% aqueous dispersion of sulfonic acid-modified polyester of min J'-1114000 was prepared using the same force γ as in Example 1 and a shorter reaction time. This polyester 10
0 IIi: After dissolving part ttt in two parts of methyl ethyl ketoshiff and 72 parts of toluene, 21% in part of 4,4'-diphenylmethanoisocyanate and dibutyltin dilaure)0
．． 1 fiit part of 051' was added and reacted at 70 to 80°C for 3 hours. The solvent was evaporated to form an aqueous dispersion containing the polyester polyurethane.

Separately, to an aqueous solution of PVA with a degree of saponification of 92% and a degree of polymerization of 650, a) a) organic boron polymer compound was added so that the ratio of PVA to the organic boron polymer compound was 1:9. ,
A complex aqueous solution was obtained by stirring at 40-50°C for 30 minutes. As the 41 boron polymer compound, (I)-8(X7
+2.1=so; P, 4=2) was used. 1. This composite aqueous solution was added to the aqueous dispersion of the above polyester polyurethane at a solid content ratio of 100:50 (small itl ratio) to obtain a liquid. Using this, Example 1
A Q uJ ffJ resin laminated film was prepared in the same manner as above.

Evaluation of Heat+1J Plastic Resin Laminated Film The surface of the resin composition layer of the film obtained in section (1) is coated with a resin whose adhesion to the film is to be tested, dried, and a resin layer with a thickness of 3 μm is formed. was formed. The resin used is
There were five types: (1) carboxymethyl cellulose, (2) polyvinylidene chloride, (2) polyvinyl acetate, (2) gelatin, and (2) cellulose acetate butyrate. To each resin solution, a red dye having good compatibility with the resin was added. The resulting resin layer was coated with a base plate [1] at 1 m intervals using a cutter knife.
A cut was made in the shape of a shape, and a peel test was conducted in the same manner as in Example 1. The remaining number of bundles is 100 for ■ and 95 for ■.
There are 100 pieces of ■, 100 pieces of ■, 90 pieces of ■,
It was found that both resins had good adhesion.

Also, as per ASTM-1894, the sliding property (coefficient of friction) is 1.
When the 1111 constant was carried out, it was 0.45, and the uncoated product was 2.0 or more -L.

Example 5 In Example 1, organic 1-poison polymer compound (I)-1
(P, = 80) to the polyester at 15 i[n
'i% and saponification degree is 88%! Organic boron polymer compound (1) in an aqueous solution of polyvinyl alcohol with a pi degree of 500
8 (X7 +Z:l =100:Ps =2)
A biaxially stretched coating film was obtained in the same manner as in Example 1, except that a coating liquid consisting of 15% M% was used, with the weight ratio of PVA and organic boron polymer compound being 1:4, Adhesion tests were previously conducted and showed very good adhesion to P, VA and PVC.

(Effect of the invention) The thermoplastic resin laminated film of the present invention thus has the following features:
Because it is constructed by laminating a thermoplastic resin film with a composition containing a composite of a specific organoboron polymer compound and polyvinyl alcohol, and a resin, it is possible to <Good adhesion to all types of equipment, and extremely good sliding properties. Therefore, this thermal 1■ plastic resin laminated film is used for recording media such as magnetic tapes, microfilms, magnetic cards, reader tapes, and floppy disks for audio, video, and computers, as well as for food, medicine, fertilizer, vapor deposition packaging, and packaging materials. Packaging applications such as plate making, tracing, membrane switches, stamping, adhesive tapes, labels, namers, OHP sheets, laminated cards, nameplates, mirrors, printing sensitive materials, printer ribbons, solar controls, adhesive bases, light shielding films, printing It is suitably used for industrial applications such as paper, PPC films, white boards, stickers, etc., as well as for agricultural applications such as agricultural greenhouses, and decorative applications such as gold and silver. In addition, even when the film is being added, it does not cause blocking and has excellent workability.

Claims (1)

[Claims] On at least one side of the thermoplastic resin film, at least one of a water-soluble resin, a water-emulsifiable resin, and a water-dispersible resin, and an organic boron polymer compound represented by the following formula (I) and/or A thermoplastic resin laminated film laminated with a composition whose main component is a composite of an organic boron polymer compound and a vinyl alcohol polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) Here, p is 10 to 10000; q is 0 or 1; when q is 1, A is -(X)_l-(Y)_m-( Z
)_n-, X and Z are oxygen-containing hydrocarbon groups with one terminal ether residue and the total number of carbon atoms is 100 or less, and Y is a ▲ group that has a mathematical formula, chemical formula, table, etc. (However, R is a hydrocarbon group having 1 to 34 carbon atoms) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R' is a hydrocarbon group having 2 to 13 carbon atoms), and l, m, and n are each independently 0 or 1
It is.