JPH01114437A - Laminate of resin films - Google Patents

Abstract

PURPOSE:To display excellent adhesiveness to any of hydrophilic polymer, hydrophilic polymer, metal, and inorganic substance, by forming a photosetting type resin modified by phosphides as at least a component of laminate resins. CONSTITUTION:A resin layer containing a photosetting type formed by reaction of at least a kind of phosphides represented by general formulae (I)-(V) (X, Y represent esterifying functional groups; R1 hydrocarbon group with a number of carbons 3-10; R2 alkyl group etc., with a number of carbon 1-12; R3 and R4 alkylene groups etc., with a number of carbons 1-12; and M alkali metal atoms etc.) is formed on at least one surface of a resin film. In this case, a polyester film or the like is used as the resin film. The photosetting type resin resulting from reaction of a phosphide represented by general formulae (I)-(V) is laminated on said resin film by coextrusion coating or another method. This process can provide a film laminate having excellent adhesiveness to all of hydrophilic polymer, hydrophobic polymer, metal, and inorganic substance.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a resin film laminate with improved adhesiveness, and in particular, is excellent for all types of adhesives such as hydrophilic and hydrophobic polymers, metals, and inorganic materials. The object of the present invention is to provide a resin film laminate exhibiting excellent adhesive properties.

[Prior Art] As is well known, resin films such as films made of polyester, polyamide, polypropylene, polycarbonate, polyetherimide, polyether sulfone, polyphenylene sulfide, polyether ester, etc.
In particular, polyester films, especially polyethylene terephthalate films, have excellent mechanical strength, heat resistance, chemical resistance, transparency, dimensional stability, etc., so they are used as base films for magnetic tapes, insulating tapes, photographic films, It is used in a wide range of applications, including tracing films and food packaging films. However, polyester films generally have low adhesive properties, so when laminating inks, electrophotographic toners, heat-sealable compositions, magnetic materials, photosensitizers, matting agents, metals, metal oxides, inorganic polymers, etc. It is necessary to perform corona discharge treatment on the surface and further provide an anchor coating agent to improve adhesion. Furthermore, when used for food packaging, the adhesiveness with the printed layer and the heat-sealing layer is weak, resulting in a low overall heat-sealing strength.

By the way, the corona discharge IA method is the most commonly used method for improving the adhesiveness of the resin film surface, and other methods include ultraviolet irradiation treatment method, plasma discharge treatment method, flame treatment method, and corona discharge treatment method under nitrogen atmosphere. Physical treatment methods such as these, chemical treatment methods such as an alkali treatment method and a brimer treatment method, and treatment methods that suitably combine the above-mentioned methods are known. However, at present, there is no known thermoplastic resin film, especially polyester film, which exhibits excellent adhesion to all hydrophilic and hydrophobic polymers and inorganic substances.

[Problems to be Solved by the Invention] The present invention has been made in view of the problems of the prior art as described above, and its purpose is to solve the problems of all hydrophilic and hydrophobic polymers, metals, and inorganic materials. The object of the present invention is to provide a resin film laminate that can exhibit excellent adhesive properties in both cases.

[Means for Solving the Problems] The structure of the resin film laminate according to the present invention is such that at least one fl of a phosphorus compound represented by the following general formulas (I) to (V) is reacted on at least one side of the resin film. The gist is that a resin layer containing a photocurable resin is formed.

GM' GM OM OM [In the formula, X and Y are ester-forming functional groups, R1 has 3 carbon atoms
-10 trivalent hydrocarbon group, R2 is an alkyl group having 1 to 12 carbon atoms, cycloalkyl group, aryl group, 1 to 10 carbon atoms
Aryl and aryloxy groups are halogen atoms, hydroxy groups, -〇M'(M'
represents an alkali metal) or substituted with an amino group. R3゜R4 is an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group, a group represented by the formula +c H20Rs1 (RIS is a group having 1 carbon number
~12 alkylene groups, cycloalkylene groups, and arylene groups are shown. m can take any value from 1 to 4. ), M represents an alkali metal atom, hydrogen, a monovalent hydrocarbon group, or an amino group] [Function] Specific examples of the phosphorus compounds represented by the above formulas (I) to (V) used in the present invention Examples include the following compounds.

NaOOHKU utI CH2O)12 Cl5
H8P-CLCH(HhOH(3) P-CH2
O) ICH20H (4) NaOOHHO0) I C) 13 P-CH, -CHCooCH, CH, OH (li)l Na0 CH2C00CH2CH20HC, HS Na0CllzCOOCHzCHzOH Rice" Low Δ side C6) 18C6H5 I lN a0
0HKO0H Na0 0HNaO0H ONa CH2-C0OHNaOCH2-C00C
H2C1 (20HONa
0KOLI ONa
OHO to OH0Na OK 0LIP (C
H2CHzCH2C)I20H) x (24)■ Na Na Na Na HOCH2CH20CH2-P-CH20CH2CH2
0H (27) 0 to 0
NaOK OLIP (
C) lzcJcH20H) 2 (37) Li P (CI2ChCHtChOH) a (38) N
a P (CH2CH2CH2CH20)1) 2 (3
9) K P (ChChOH) 2 (40) OH OHOH P (CH2CH2CH2CH20H) x (43
)l H NaO ■ HOCH2Ch-P-ChCOOCHzClhOH(4
4) Basket Na HOCH2CHz-P-C)l*cHzcOO1((4
5) Na ■ l0C) I2CHzOCH2-P-ChOCHzCHz
OH(4B)Na)100cc82c)1*ChOC1b-P-CH20
CH2C1hCOOH(413)HOCH2CH20C
Hi-P-CHzOCHzClhOH(49)c2os HOCH2CH20CH2-P-CH20CH2CH2
0H (5G) NaONa0 NaONa0 NaO to O 2HsO 0-P-CHaCHiOH (57) IO -cans ■ 0-P-CH2ChCOOCHs (58) NaO Photocuring that constitutes the main component of the laminated resin layer in the laminate according to the present invention The type resin is a phosphorus-containing photocurable resin that has at least one photofunctional group in the molecule and is reacted with at least one of the phosphorus compounds shown in the formulas (I) to (V), Specific examples of the base resin include (A) an acrylic double bond-containing compound and (B) at least one of urethane bonds, ester bonds, ether bonds, and amide bonds.
Examples of resins that are bonded via seed bonds include polyurethane acrylate resins, polyester acrylate resins, and epoxy acrylate resins. Note that the acrylic double bond refers to residues (acryloyl group or methacryloyl group) of acrylic acid, acrylic ester, acrylic amide, methacrylic acid, methacrylic ester, methacrylic amide, etc.

The phosphorus-containing photocurable resin containing the above-mentioned specific phosphorus compound can be manufactured through various processes. It can be obtained by reacting the phosphorus compounds shown in formulas (I) to (V) above as components. In particular, when producing polyester/polyol, the phosphorus compounds represented by the above formulas (I) to (V) may be added at any stage before the completion of polymerization of the polyester/polyol to cause the reaction. In this case, the phosphorus compound is preferably added after the transesterification reaction or after the esterification reaction from the operational point of view during production.

In addition, the above specific phosphorus compounds include polyurethane/acrylate resin, polyester/acrylate resin, epoxy/
For example, it can be used as a component of photocurable resin raw materials such as acrylate resins and acrylate compounds.
In the case of phosphorus compounds containing hydroxy groups, polyurethane and
Acrylate resins can be produced.

Furthermore, among the above-mentioned specific phosphorus compounds, diols are used as chain extenders for polyurethane/acrylate resins, dicarboxylic acids are used as chain extenders for epoxy/acrylate resins, and diols/dicarboxylic acids are used as chain extenders for polyester/acrylate resins. Among these other specific phosphorus compounds, mono(meth)acrylates of diols may be used as chain extenders for polyurethane acrylate resins, and monoethyloxy(meth)acrylates of dicarboxylic acids may be used as extenders. It may be used as a terminal capping agent for epoxy acrylate resins, and poly(meth)acrylates of specific phosphorus compounds can also be used as acrylic compounds.

The photocurable resin according to the present invention is produced by mixing an acrylic double bond-containing compound and a raw material containing a specific phosphorus compound and/or a raw material resin reacted with a specific phosphorus compound in a solvent or without using a known method. Obtained by reaction in a solvent. The preferred molecular weight of the resulting resin is 500 to 10
It is 0,000.

It is appropriate to use the phosphorus compound represented by the above-mentioned formula (V) in such a way that the total resin contains 1,100 ppm to 50,000 ppm of phosphorus atoms; On the other hand, if it exceeds the above range, problems such as increased hygroscopicity, decreased physical properties, and decreased adhesion to thermoplastic resin films will occur.

In addition, in manufacturing the above photocurable resin, the formula CI)
In addition to the phosphorus compounds (V), the following hydrophilic polar group-containing compounds may be copolymerized, or the above compounds may be mixed as another copolymer.

Parent group -N''- possessed by a hydrophilic polar group compound other than a phosphorus atom
Rs , -Ca Ha Rt , -3OI M (wherein M represents a hydrogen atom, an alkali metal, a tetraalkylammonium, a tetraalkylphosnium, and R1 to Rs
is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group,
) representing an aralkyl group.

Specific examples of compounds containing these hydrophilic polar groups are as follows.

(I)-COOM Polycarboxylic acids, glyceric acid, dimethylolpropionic acid, N,N-jetanolglycine, hydroxycarboxylic acids such as hydroxyethyloxybenzoic acid, aminocarboxylic acids such as diaminopropionic acid, diaminobenzoic acid, and their like. derivatives etc.

Nitrogen-containing alcohols and derivatives thereof, such as N-methylgetanolamine, 2-methyl-2-dimethylaminomethyl-1,3-propanol, and 2-methyl-2-dimethylamino-1,3-brobanediol.

(3) 2nd grade engineering J-uni” b.

Pyridine ring-containing compounds such as picolinic acid, dipicolinic acid, aminopyridine, diaminopyridine, hydroxypyridine, dihydroxypyridine, aminohydroxypyridine, pyridinyldimethator, pyridinylpropanediol, pyridinylethanol, and derivatives thereof.

(4) Polycarboxylic acids and derivatives thereof such as 5-sodium sulfoisophthalic acid, 5-tetrabutylsulfonium, sulfoisophthalic acid, sodium sulfosuccinic acid, sodium sulfohydroquinone and its alkylene oxide adduct, sodium Sulfobisphenol A and its alkylene oxide adducts, etc.

Next, examples of the resin film (base film) on which the phosphorus compound-modified photocurable resin is laminated include polyester film, polyamide film, polycarbonate film, polyphenylene sulfide film, polyetherimide film, polyether sulfone film, etc. The most suitable one is selected and used each time depending on the intended use and required characteristics of the final film laminate, but the most common are polyester film, polyamide film, polycarbonate film, etc.

Methods for laminating the photocurable resin reacted with the phosphorus compounds of formulas (I) to (V) on the thermoplastic base film include a coextrusion coating method, an extrusion lamination method,
There are coating methods, dry lamination methods, hot melt adhesion methods, etc., and any method may be used. It is of course possible to perform stretching or heat treatment before or after lamination, if necessary. The thickness of the phosphorus compound-modified photocurable resin (hereinafter simply referred to as "modified photocurable resin") to be laminated is arbitrary, but from the viewpoint of providing adhesiveness, it is preferable to be as thin as possible. Curable resin has flame resistance, but this effect becomes noticeable when the phosphorus atom content exceeds 10,000 ppm, so in some cases, the modified photocurable resin layer may be made thicker than the base film layer. It is also effective to improve flame resistance.

In producing the film laminate of the present invention, adhesion can be further improved by performing corona discharge treatment or ultraviolet irradiation treatment in an air or nitrogen atmosphere before and after lamination.

The film laminate thus obtained is used as an information recording film, a packaging film, an electrical film, and other films. In particular, film laminates containing polyester resin as a constituent material of the base film can be used as base films for magnetic recording, base films for printing,
It can be widely used as a base film for capacitors, a film for food packaging, a base film for vapor deposition, etc.

When used in the above applications, if necessary, other polymers, colorants, antistatic agents, crosslinking agents, etc. may be added to the modified photocurable resin layer.
Anti-blocking agents, lubricants such as inorganic or organic particles, ultraviolet absorbers, photodegradation inhibitors, and other additives may be added to the extent that the effects of the present invention are not impaired.

The additives include water-soluble, organic solvent-soluble or oil-soluble dyes and pigments, and insoluble dyes and pigments.

Examples of the antistatic agent include anionic, nonionic, and cationic surfactants, polyether groups, polymers containing anionic or cationic groups, and conductive particles made of metals or metal oxides.

As a crosslinking agent, a compound containing two or more functional groups capable of reacting with active hydrogen, such as an alkoxy group, an alkylol group, an isocyanato group, an epoxy group, an azirinyl group, a (meth)acroyl group, an alkoxyalkyl group, etc. is included.

As anti-blocking agents, higher fatty acids and their salts,
Includes esters, amides, amines, mineral oils, silicones, fluorine compounds, etc.

Examples of lubricants such as inorganic or organic particles include silica-based, calcium carbonate-based, kaolin-based, barium sulfate-based, titanium-based, talc-based, benzoguanamine, polyolefin-based, melamine-based, polyacrylic acid ester-based, polyamide-based,
These include polyester-based, polycarbonate-based, etc., and these may be surface-treated, and the particle size may be arbitrarily selected depending on the application.

Examples of the ultraviolet absorber include benzophenone, salicylic acid ester, and triazole.

Photodegradation inhibitors include various compounds such as phenolic, epoxy, sulfur-containing, phosphorus-containing, nitrogen-containing, metal-containing, and conjugated double bond-containing compounds.

Additives other than those mentioned above include antifogging agents, flame retardants, and the like.

Further, in the present invention, if necessary, in addition to the modified photocurable resin, other resins having compatibility with the resin, such as vinyl chloride resin, polyester resin, cellulose resin, acrylic resin, epoxy resin, phenoxy resin, may be used. ,
It is also possible to use polyvinyl butyral, acrylonitrile-butadiene copolymer, etc. together, or to use other resins together. Furthermore, before applying the film laminate of the present invention to the above-mentioned uses, desired film properties may be imparted by laminating or anchor coating another resin on the modified photocurable resin side of the laminate. It is possible.

The film laminate of the present invention is produced by laminating a photocurable resin (and other resins as necessary) on a thermoplastic resin film as described above, and then calendering the laminate as necessary. It can also be treated with radiation. As the light irradiated to cure the photocurable resin layer, in addition to electron beams, radiation such as neutron beams and γ rays, or visible to ultraviolet rays can be used, and the irradiation amount of ultraviolet rays is about 1 to 10 Mrad is preferred, particularly about 2 to 8 Mrad.

The film laminate according to the present invention comprises a photocurable resin modified with a phosphorus-containing compound as at least one component of the laminate resin, as described above, so that the film laminate after light irradiation is made of a wood-philic polymer. , hydrophobic polymer,
It exhibits excellent adhesion to both metals and inorganic materials, and by taking advantage of this feature, it can be used in a wide range of applications.

[Example] Next, the present invention will be specifically explained with reference to Examples. In the examples, "parts" indicate parts by weight.

Example 1 In an autoclave equipped with a thermometer and a stirrer, 485 parts of dimethyl terephthalate, 485 parts of dimethyl isophthalate, 409 parts of ethylene glycol, 485 parts of neopentyl glycol and 0 parts of tetrabutoxy titanate were added.
．． Then, 50.1 parts of the phosphorus compound shown as the above formula (B) was charged, and 220 to 230
The reaction was carried out for an additional hour at ℃. Next, the temperature of the reaction system was raised to 250° C. over 30 minutes, and the pressure of the system was gradually lowered to 10 mmHg after 45 minutes, and the reaction was continued under these conditions for an additional 60 minutes. The obtained polyester diol A had a molecular weight of 2500 and a phosphorus content of 1600 ppm.

After dissolving 100 parts of this polyester diol A in 72 parts of toluene and 72 parts of methyl ethyl ketone, 4.4
Add 21 parts of '-diphenylmethane diisocyanate and 0.05 part of dibutyltin dilaurate to 70-80°C.
The mixture was allowed to react for 3 hours. 15 parts of pentaerythritol triacrylate was added to this reaction solution and reacted at 70 to 80°C for 2 hours, and then 2-methyl-2dimethylamino-1
゜7.1 parts of 3-propanediol was added and reacted for another 5 hours until the solid content concentration was 40! A polyurethane acrylate resin solution of i amount % was obtained. The molecular weight of the obtained polyurethane acrylate resin A was 1500 G, and the phosphorus content was 1 l 100 pp.

This polyurethane acrylate resin solution was mixed with toluene/
After diluting with a mixed solution of methyl ethyl ketone (weight ratio 50150) to adjust the solid content concentration to 5% by weight, it was coated on a polyester film using an air knife method and dried at 120°C to form a coating with a coating weight of 0.3g10+2. A polyester film was obtained. After that 5Mra
The polyurethane acrylate resin layer was cured by the radiation treatment in step d, and the desired film laminate was obtained.

Comparative Example 1 The acid components of the polyester copolymer composition constituting the radiation-curable resin were 35 mol% of terephthalic acid, 35 mol% of isophthalic acid, and 30 mol% of adipic acid, and the glycol components were 50 mol% of ethylene glycol and neopentyl. A film laminate was obtained in the same manner as in Example 1, except that 50 mol% of each glycol was used (no phosphorus-containing compound was used) and toluene/methyl ethyl ketone (weight ratio, 50150) was used as a solvent.

Comparative Example 2 An uncoated polyester film was used as is. The adhesion of each film laminate (or single layer film) obtained in Example 1 and Comparative Example 1.2 to various polymers, metals, and inorganic substances (magnetic agents) was examined by the following method.

(Adhesion to polymers) After adding a red dye that is highly compatible with each polymer to ■polyvinyl alcohol, ■polycarbonate, ■alcohol-soluble nylon, ■gelatin, or ■cellulose acetate butyrate, a thick layer is applied onto each test film. 3μ
The adhesive tape was coated to give an angle of m, and Nichiban cellophane tape was applied and peeled off at a peeling angle of 18Q° to check for peeling. 10. No peeling at all. 5. Half peeled. Those that were completely peeled off were ranked as 1.

(Adhesion to metal) Aluminum was vapor-deposited on the coating layer side of each test film,
This was immersed in water at 100°C for 30 minutes and then taken out.
A test was repeated 10 times in which the tape was pressure-bonded to the vapor-deposited surface and rapidly peeled off, and the adhesiveness was evaluated in the same manner as above.

(Adhesion to lift agent) Magnetic γ-Fe20. 250 parts of fine powder particles, 2 parts of dioctyl sulfonate, copolymerized polyester (acid component: 45 mol% terephthalic acid + 20 mol% isophthalic acid +
32.5 mol % of sebacic acid + 2.5 mol % of 5-sodium sulfoisophthalic acid, glycol component: 600 parts of ethylene glycol 5-rotate were mixed for about 24 hours using a ball mill. 400 parts of this mixture and 1 part of copolyester resin
00 parts of nitrocellulose, 70 parts of vinyl chloride-vinyl acetate copolymer, 30 parts of polyisocyanate, 400 parts of methyl ethyl ketone, and 400 parts of cyclohexane were added and mixed for about 70 hours using a ball mill again. It was coated on each of the above films so that the thickness was 2 μm.

After making 100 crosscuts on the surface of the coated magnetic layer, adhesive tape was pasted on the surface, applied uniformly to the entire surface, and then instantly peeled off 5 times to observe the adhesion state. Adhesion was evaluated based on the number of remaining crosscuts.

The results are shown in Table 1, and it can be seen that the laminated films of Examples have very excellent adhesion to various polymers, metals, and magnetic agents.

Table 1 Example 2 Terephthalic acid 70 mol%, isophthalic acid 2 as acid components
5 mol%, adipic acid 5 mol%, ethylene glycol 70 mol%, diethylene glycol 26 mol% as a glycol component, compound 4 of the above formula (54) as a phosphorus compound.
A radiation-curable resin solution was prepared in substantially the same manner as in the example except that the respective mole % was used, and then the solvent was distilled off to obtain granules of the resin.

300 parts of the above granular resin and 140 parts of n-butyl cellosolve were stirred in a container at 150 to 170°C for about 3 hours to obtain a uniform and viscous melt. 560 parts of water was gradually added to this melt and stirred for about 1 hour to obtain a uniform pale white aqueous dispersion having a solid content concentration of 30%.

Add 4500 parts of water and 450 parts of ethyl alcohol to this aqueous dispersion.
0 parts was added to dilute it to obtain a coating liquid with a solid content concentration of 3%.

This coating solution was applied onto an unstretched polyester film so that the solid content was 1 g/m', and the film was heated at 90°C in the longitudinal direction.
Stretched 3.5 times at
After double stretching, it was heat treated at 210 DEG C. and the resulting film laminate with a coating thickness of O, 1 g/n' and a base layer of 50 .mu.m was subjected to radiation treatment of 5 M rad.

A-1 Cure KK Red (manufactured by Nagase Screen Co., Ltd.) was screen printed on the coat layer side of this treated film so that the printing thickness was 10-15 μm, and irradiation was performed using an ultraviolet irradiation device with a cumulative irradiation energy of 1500 rnJ/cra2. Ta.

When 100 substrates were placed on this printed surface and a cellophane tape peeling test was performed, no peeling was observed.

[Effects of the Invention] The present invention is configured as described above, and by laminating radiation-curable resins modified with a specific phosphorus-containing compound and curing them with radiation, wood-philic polymers, hydrophobic polymers,
It has become possible to provide a film laminate that has excellent adhesion to all metals and inorganic substances.

Claims (1)

[Claims] At least one side of the resin film has the following general formula (I).
A resin film laminate comprising a resin layer containing a photocurable resin reacted with at least one of the phosphorus compounds represented by (V). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) [In the formula, X and Y are ester-forming functional groups, R_1 is a trivalent hydrocarbon group having 3 to 10 carbon atoms, and R_2 is a carbon number 1 to 12
represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group having 1 to 12 carbon atoms, a cycloalkoxy group, or an aryloxy group. The aryl group and aryloxy group may be substituted with a halogen atom, a hydroxy group, -OM'(M' represents an alkali metal), or an amino group. R_3 and R_4 have 1 carbon number
~12 alkylene group, cycloalkylene group, arylene group, group represented by the formula ■CH_2OR_5■_m (R_5 represents an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an arylene group. m is 1 to 4) ), M represents an alkali metal atom, hydrogen, a monovalent hydrocarbon group, or an amino group]