JPH04183716A - Resin composition and laminated film - Google Patents

Abstract

PURPOSE:To obtain the subject composition, composed of a charge-transfer type combination prepared by reacting semipolar organoboron bonds having specific recurring units with an amino compound, capable of imparting antistatic properties and easy adhesion and useful for packaging applications, etc. CONSTITUTION:The objective composition is composed of a charge-transfer type combination which is a semipolar organoboron bond-containing polyester, composed of recurring units expressed by formulas I and/or II (R1 and R2 are polyester residue having 300-10000 molecular weight) and containing part or all of the aforementioned semipolar organoboron bonds reacted with an amino compound. Furthermore, the polyester expressed by formula I is preferably obtained by reacting, e.g. a polyester having 1,2-glycol bonds at both terminals with at least one boron compound selected from boric acid, boric acid triesters and boric anhydride.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a resin composition and a laminated film, and more specifically, the present invention relates to a resin composition and a laminated film, and more particularly, to a resin composition and a laminated film having properties that can provide antistatic properties and easy adhesion. This invention relates to a laminated thermoplastic film with excellent adhesive properties and adhesive properties.

(Prior art) 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 magnetic. Widely used for tape base films, insulating tapes, photographic films, tracing films, food packaging films, etc.

However, these thermoplastic resin films are
Thermal iJ plastic resin itself is an insulator, so it is easily charged by static electricity, and its surface is highly crystal oriented, so it has the disadvantage of poor adhesion to various inks and adhesives. There is. Therefore, various methods have been used to impart antistatic properties to thermoplastic resin films or to improve their adhesion properties. Methods of imparting antistatic properties include kneading conductive substances such as antistatic surfactants, ionic compounds, metal powders and metal oxides into thermoplastic resins, and applying coatings. The method used was to mix it in and apply it.

In addition, methods for imparting easy adhesion include treating the film surface with active rays such as corona discharge and ultraviolet plasma, and applying various easily adhesive resins such as polyester and polyurethane as a primer layer. Ta.

Among these methods, the method of adding the above-mentioned antistatic properties imparting agent into the primer layer is one that imparts antistatic properties and easy adhesion properties at the same time.t5. This is a useful method because it allows you to

However, the method using a surfactant or an ionic compound as an antistatic agent has a problem in that the antistatic property in an environment of low γ8 degrees is reduced.

- On the other hand, the h method, which uses conductive substances, does not have the problem of low antistatic properties even in low humidity environments, but in order to provide antistatic properties, it is necessary to add a large amount of conductive material in the primer layer. Since it is necessary to add an adhesive substance, there is a problem that the effect of imparting adhesiveness is reduced.

The method using the conductive material has problems such as poor transparency and high cost.

Under these circumstances, new types of antistatic agents are being developed. As one such antistatic agent, a polymer charge transfer type conjugate, which is a reaction product of a semipolar organic boron polymer compound and a tertiary amino having a limited hydroxyl group, has been proposed. (Unexamined Japanese Patent Publication No. 1-18539
This antistatic agent certainly has superior properties to conventional antistatic agents in that it exhibits high antistatic properties even in a low humidity environment, and is suitable for use in R1. however,
The antistatic agent has the drawbacks of being sticky and having low adhesion properties.

Under such circumstances, it has been desired to develop a resin composition that can provide both antistatic properties and easy adhesive properties, and a thermoplastic resin film that has both antistatic properties and easy adhesive properties.

(Problems to be Solved by the Invention) In view of the above-mentioned circumstances, the present invention provides a resin composition having properties that can impart both antistatic properties and easy adhesive properties, and a resin composition that has both antistatic properties and easy adhesive properties. The purpose of the present invention is to provide a thermoplastic resin film that has the following features.

(Means for Solving the Problems) That is, the present invention provides a semipolar organic boron bond-containing polyester consisting of the following repeating units (I) and/or (II), in which some or all of the semipolar organic boron bonds are A laminated film formed by laminating a polyester resin composition characterized by a charge transfer type bond reacted with an amino compound and a thermoplastic resin film (both of which are laminated on one side of the polyester resin composition).

(In the formula, R3 and R2 have a molecular weight of 300 to 1°000.
Polyester residue) Examples of the method for producing the semipolar boron bond-containing polyester in the present invention include the following method.

The polar organic boron bond-containing polyester of structural formula (I) is a polyester having 1,2 glyph bonds at both ends, and a boron compound of at least IN selected from boric acid, boric acid triester, and boric anhydride. Synthesized by reaction with

An example of a synthetic route using boric acid is shown below.

(Synthesis route A) HOCH-CB2O-R, -QC■2- CHOH11
0CH2CH20H (In the formula, R is a polyester residue with a molecular weight of 300 to 10,000) In the first step of the reaction, both ends and hydroxyl group and 3-
The reaction with ox-7 propylene oxide is carried out by adding the raw material into a solution of a polyester having hydroxyl groups at both ends diluted 2 to 20 times with an aliphatic stone or aromatic chemically inert petroleum solvent. 0 for polyester. O1~5
([1)%, preferably 0.05 to 1 (i amount)% of a Lewis acid other than a protic acid (e.g., boron trifluoride, etherate, aluminum chloride, tin chloride, etc.) as a catalyst. After adding, at normal pressure, 50-20
3-oxypropylene oxide is injected at 0°C, preferably 100-150°C, and the reaction is allowed to proceed in the same temperature range.

In the second step, the reaction with boric acid, an aqueous boric acid solution diluted to 10% (by weight) or less, preferably 1 to 5% (by weight), and a solution of the reaction product in a petroleum solvent in the first step. 1(
mol): 1-1.1 (mol) after the raw material preparation ratio is brought into contact, under normal pressure, 100-150°C, preferably 11
By carrying out azeotropic dehydration at 0-120°C, interfacial condensation polymerization is carried out smoothly, and the reaction product No. 21 is successfully produced.

The semipolar organoboron bond-containing polyester of structural formula (n) can be obtained by the same method as above (/J method a) or by the reaction of a polyester having a carboxyl group end with a diol containing a polar organoboron compound (method b). It is synthesized by etc.

An example of a synthetic route for method a is shown below.

(Synthesis route B) An example of the synthetic route of the method is shown below.

(Synthesis route) C) The first step in method a, the reaction between the carboxyl groups at both ends and 3-ox7propylene oxide, differs from the reaction with the citroxyl groups at both ends described above, and does not necessarily require the use of a catalyst. The reaction often proceeds even under non-catalytic conditions.

The second step in method a, the reaction with boric acid, may be carried out in the same manner as described above.

The method can be synthesized using an azeotropic dehydration method similar to the reaction with boric acid described above in a petroleum solvent solution system.

In this case, lower alcohol having 1 to 4 carbon atoms is added in an amount of 5 to 50% (%, preferably 10 to 50%, preferably 10 to 50%) based on the raw material polyester.
The reaction may progress more easily if 15% (by weight) is added and azeotropic dehydration is carried out while also performing transesterification during the reaction.

The following methods 1-1 are shown as examples, and are not limited to these methods.

R1 and R2, which are polyester components constituting the semipolar organic boron bond-containing polyester in the present invention, are:
It is produced by condensation polymerization of one or more dicarboxylic acids and diols by a conventional method. As acid components, terephthalic acid, isophthalic acid, phthalic acid, 1,4-
naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, naphthalic acid,
Biphenyldicarboxylic acid, 1,2-bis(phenoxy)
Aromatic dicarboxylic acids such as ethane-p,p'-dicarboxylic acid and their anhydrides or ester-forming derivatives, p-hydroxybenzoic acid, p-(2-hydroxy/
Examples include aromatic hydroxycarboxylic acids such as ethoxy/)benzoic acid 3 and ester-forming derivatives thereof. In addition, examples of aliphatic (cyclic) dicarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sepanonic acid, maleic anhydride, and fumaric acid, 1.3-7 clobentanedicarboxylic acid, and 1.4 -7 Alicyclic dicarboxylic acids such as chlorohexanecarboxylic acid and their anhydrides, or
Examples include ester-forming derivatives.

Glycol components include ethylene glycol, propylene glycol, 1.3-7"ropansiol, 1.4
-butanediol, 1,5-bentanediol, 1,6
- Aliphatic diols such as hexanediol, dipropylene glycol and polyethylene glycol, alicyclic diols such as 1.4-/chlorohexanediol and 1.4-cyclohexane dimetatool, bisphenol A1 hydroquinone and their alkylene okindo additions Examples include diols such as diol.

The polyester polyol or polyester polycarboxylic acid used in the present invention is usually preferably a linear polymer, but this does not preclude the use of polyfunctional components. Such polyfunctional components include trimellitic acid, pyromellitic acid,
Polycarboxylic acids such as cyclohexanetricarboxylic acid and their anhydrides or ester-forming derivatives, glycerin, trimethylolethane, trimethylolpropane.

Examples include polyols such as pentaerythritol.

Furthermore, introducing a hydrophilic group into the polyester component is also effective and recommended as a means for imparting water solubility or water dispersibility to the composition.

Compounds containing hydrophilic groups and group groups suitable for such purposes are illustrated below.

(1) -GOON (M represents a hydrogen atom, an alkali metal, tetraalkylammonium or tetraalkylsulfonium) polycarboxylic acid, glyceric acid, dimethylolpropionic acid, etc.

■ Nitan J (M has the same meaning as l.) Polycarboxylic acids such as 5-sodium sulfoisophthalic acid, sulfoisophthalic acid, and sodium sulfosuccinic acid,
and derivatives thereof; sodium sulfohydroquinone and its alkylene oxide adduct; sodium sulbobisphenol A and its alkylene oxide adduct.

(3) - and l] 11 groups - -R4--R4+ I R5P (I[[)-1R5-P R0(rf
l)-2ON, ON.

R6- R5-0-P R0(III)-5 ON.

(R4 is a trivalent hydrocarbon group having 3 to 1 carbon atoms; R5 is an alkyl group having 1 to 12 carbon atoms, a 7-chloroalkyl group, an aryl group, an alkyl group having 1 to 12 carbon atoms, a cycloalcoquine group, or an aryl group having 1 to 12 carbon atoms; an oxy group [the aryl group and the aryloxy group are a halogen atom, a hydroxy group, -0M2 (M2 represents an alkali metal)];
R6 and R7 are each an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group, or a group of the formula (C
H20Re) a group represented by r (Rs has 1 to 12 carbon atoms)
represents an alkylene group, represents a cycloalkylene group or an arylene group, r is 1 to 4); and Ml represents an alkali metal atom, hydrogen, a monovalent hydrocarbon group, or an amino group] Eight of these polyesters have a molecular edge of 3 as calculated by the end group measurement method.
Must be between 00 and 10,000. 500～
5,000 is particularly preferred.

If the molecular weight is less than 300, the effect of imparting adhesiveness will be reduced, which is not preferable.

On the other hand, if it exceeds to or ooo, the adhesion imparting effect will be saturated,
Moreover, the effect of imparting antistatic properties is reduced, which is not preferable.

The amino compound used to form the composite with the semipolar organic boron-containing polyester may be primary, secondary, or tertiary. Further, it may be any of aliphatic, alicyclic, aromatic, and heterocyclic.

Further, it may have other bonding groups such as a hydroxyl group, an alkoxyl group, an ether group, and a halogen group.

For example, methylamino, dimethylamino, trimethylamino, ethylamino, diethylamino, triethylamino, butylamino, dibutylamino, tributylamino, hexylamino, diethylamino, trihexylamino, ethanolamino, jetanolamino, triethanolami7, fatty ethylene oxide adducts and propylene oxide adducts of primary and secondary aminos of the group;
Examples include ncrohequinone, piperidine, morpholine, pyridine, and lucidine. These amino compounds may be used alone or in combination of two or more.

Particularly preferred are those having a pKa of 7 or more. Therefore, aliphatic and alicyclic compounds are recommended.

When forming the complex, the molar ratio of the semipolar boron bond and the amino compound is not particularly limited, but the ratio of the basic nitrogen atom to one semipolar boron bond should be 0.1 to 1. It is preferable to do so.

The complex is formed by charging it into a closed or closed reactor, under normal pressure, at 20 to 200°C, preferably at 50 to 15°C.
It is produced by reacting at 0°C. At this time, the reaction can be carried out more easily if a polar solvent such as alcohol, ether, or ketone is present.

As the base film used in the laminated film of the present invention, any thermo6I plastic resin having any film-forming ability may be used.
Are there any particular restrictions? Polyolefin resins such as polyethylene/, polypropylene/etc., polyethylene terephthalate, polyethylene isophthalate, polyethylene 2. E3
- Polyester resins such as naphthalate, polybutylene terephthalate and their copolymers, polyether resins such as polyoxymethylene, nylon-6, nylon-66, polymethaxylylene adipamide Polyamide resins such as polystyrene, poly(meth)acrylic acid esters, polyacrylonitrile, vinyl resins such as polyvinyl acetate and their copolymers, polycarbonate resins, cellophane, acetate, etc. In addition to cellulose resins such as polyimide, polyetherimide, polyphenylene sulfide, polyether sulfone, polysulfone, polyether ketone, polyether ketone ketone, fluorine-containing polymers, and many other resins, Examples include oriented films made of polymers, copolymers, mixtures, and laminates, which are unstretched or uniaxially or biaxially stretched.

Among them, the first aspect of the present invention is that the base film is made of two-wheel stretched polypropylene, polyester,
A film made of polyamide is preferred. Particularly suitable is polyester film.

The thickness of the film is not particularly limited, and is usually 1 to 2.
50u, and as a packaging material, it is particularly preferable that it is 3 to 50u.

This base film may be a single film or a composite multilayer film, and the combination method and number of layers in the multilayer film are arbitrary.

The essence of the present invention is that a layer containing a polyester resin composition containing the above-mentioned charge transfer type bonding body is laminated on at least one surface of such a thermoplastic resin film.

The laminated component may be only a polyester resin composition containing the above-mentioned charge transfer type bond, or may include other polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, vinyl chloride resins, vinylidene chloride resins, etc. It may also be a blend with other known resins such as resins.

In addition, if necessary, add coloring agents, other anti-static agents (antistatic agents, cross-linking agents, anti-blocking agents, lubricants using particles of inorganic or organic materials, etc.), organic lubricants, ultraviolet absorbers, deterioration inhibitors, etc. These additives may be contained in proportions that do not impair the properties of the obtained film.Among the above additives, the crosslinking agent improves the adhesion, water resistance, and water resistance of the resin composition layer (coating layer). Added to improve solvent resistance and scratch resistance.Such crosslinking agents include Epoquine resins, blocked incyanate resins, vinyl resins, acrylamide resins, polyamide resins, melamine resins, and methylolated resins. Various resins such as urea resins and alkylolated urea resins; silane-based and titanium-based coupling agents, etc.

The laminate is preferably formed by dissolving or dispersing the above composition or a blend of the composition and other components in a suitable solvent and coating the solution on the surface of the film.

'? ! When L'' or M is a dispersion liquid, there is no restriction in applying means such as dispersion treatment.

There are no restrictions on methods such as adding a surfactant to the two-component coating in order to improve coating properties.

A coating liquid containing this composition is applied to the surface of the base film.

Here, the base film may be an unstretched film or a uniaxially or biaxially stretched film, but it is preferable that the base film is further stretched -axially or biaxially in a predetermined direction after coating.

For example, there is a method in which polyester is melt-extruded, cooled and solidified, applied to a casting material, and then biaxially stretched in the transverse direction and then in the longitudinal direction. A recommended method is to then stretch the film in the transverse direction to obtain a biaxially stretched film.

■-Specific coating 1 of the coating solution No. 17J1 includes roll coating method, gravure coating method, roll brushing method, spray coating method, air knife coating method, impregnation method,
One example is the curtain coat method. These methods are
Can be used alone or in combination.

The coating amount of the composition is usually 0.003 to 5 g/e11, preferably 0.01 to 3 g/111' solid content on one surface of the final biaxially stretched film.

Conditions for orientation crystallization of the polyester film, such as stretching and heat setting, can be carried out under conditions conventionally accumulated by those skilled in the art.

In the present invention, the composition can be applied to one side or both sides, but a method in which the composition is applied to one side is recommended because a characteristic of the method of the present invention is that the reflection chamber on the coated side is also free from charge.

(Function) Regarding the present invention, we will now discuss the mechanism of action by which a polyester resin composition comprising a charge transfer type bond obtained by the reaction of a semipolar organic boron bond-containing polyester and an amino compound exhibits an antistatic effect. Then, as shown in the reaction formula below, when the semipolar bond part of a given semipolar organic boron bond and the basic nitrogen bond to form an ion pair in each segment, the acid proton generated moves in a manner that leaves bonding properties on both the boron side and the nitrogen side, resulting in a resonance structure and the movement of multiple electrons within the entire polymer volume. We speculate that this is the driving force that imparts a Fermi level to the insulating element material that is in contact with the charge-transfer type bonding body, allowing it to transform into something with the electrical properties of a semiconductor.

(Example) Next, Examples and Comparative Examples of the present invention will be shown.

The measurement and evaluation methods used in the present invention are shown below.

l) Measurement of molecular song of polyester component 2) Apply a vinyl chloride-vinyl acetate copolymer solution colored with an adhesive red dye so that the coating thickness after drying is 3 μm, and use a cutter knife to cut 1 mm onto the coated surface. Incisions were made in the base cane at intervals to form 100 squares.

Cellophane tape (L-back, manufactured by Nichihan Co., Ltd.) was applied evenly to the coated surface, and then the tape was quickly peeled off in a 180 degree direction. After repeating the peel test three times, the same number of squares remaining was counted.

3) Surface specific resistance Applied voltage 500V, 2 using a specific resistance measuring device manufactured by Takeda Riken Co., Ltd.
Measurement was carried out under the conditions of 3° C. and 50% RH.

4) Triboelectrification Testing was carried out in accordance with JIS-L-1094 using a Kyoto University Kaken rotary static tester (R8T-201) manufactured by Ikkoa Shokai.

The friction body uses a stainless steel plate and has a load of 500gf.

Measurement was performed at 23° C.-50% RH.

The saturation voltage (V) immediately after rubbing for 1 minute and the voltage (V2) after 30 seconds had elapsed were measured.

The attenuation rate (D) was calculated as follows.

Example 1 Examples 1 to 4 A) Synthesis of polyester Dicarboxylic acid unit power, terephthalic acid 5 by transesterification method
0 mol%, 45 mol% of isophthalic acid and 5 mol% of 5-sodium sulfoyl/phthalic acid, and the glycol units are composed of 80 mol% of ethylene glycol and 20 mol% of neopentyl glycol. A hydroxyl-terminated polyester was synthesized. The polyester was reacted with phthalic anhydride to synthesize a polyester having carboxyl groups at both ends.

B) Synthesis of semipolar organoboron bond-containing polyester and charge transfer type conjugate Synthesis of semipolar organoboron bond-containing polyester (GPC molecular weight approximately 20,000), water-
Reactions with various amino compounds were carried out under the dotted line in a mixed solvent of methyl ethyl ketone to obtain charge transfer conjugates 1 to 4 shown in Table 1.

C) Production of laminated polyester film Polyethylene terephthalate is melt-extruded at 280 to 300°C, cooled with a cold roll at 15°C to obtain an unstretched film with a thickness of 150°C, and this unstretched film is extruded at different speeds of 85°C. 3.5 °C longitudinally through a pair of rolls
Stretched twice. A coating solution in which the charge transfer bond synthesized by method B) was dispersed in a water-itubrobanol solvent was applied to the surface of this film using an air knife method, and the film was dried with hot air at 70°C. This film was stretched 3.5 times in the transverse direction at 98°C using a tenter, and then heat-set at 200-210°C to form a biaxially stretched laminate film with a thickness of 12μ (laminate layer 0.15/JJI). Obtained.

Table 2 shows the properties of the obtained laminated film.

The laminated films obtained in these Examples have good adhesive properties and antistatic properties. Furthermore, the laminated film obtained in this example also has antistatic properties on the non-laminated side, and has the extremely interesting property that antistatic properties can be imparted to the entire laminated film by laminating only one side. ing.

That is, the surface resistivity of the non-laminated surface is as high as that of a normal polyester film, but the triboelectric charging property is improved to the same level as that of the laminated surface.

Examples 5 and 6 ^) Charge transfer type conjugate A semipolar organoboron bond-containing polyester was synthesized (GP
The charge transfer type conjugates of 5 and 6 shown in Table 1 were obtained in the same manner as in Examples 1 to 4.

B) Production of It layer polyester film The properties of the laminated film obtained in the same manner as in Examples 1 to 4 are shown below, except that the coating liquid was a dispersion of the charge transfer type bonded substance dispersed in a water-itbrobanol solvent. Shown in 2.

The laminated films obtained in these Examples also have excellent adhesive properties and antistatic properties.

Example 7 A charge transfer type compound synthesized by the method of Example 6 by reducing the addition hole of amino/compound so that the reaction amount of the amino compound was 0.3 mol per mol of semipolar organoboron-containing lighted polyvarnish. Table 2 shows the properties of a laminated polyester film obtained in the same manner as in Example 6, except that the bonded body 7 was applied as a coating liquid.
nihosu.

The laminated film obtained in this example also has excellent adhesive properties and antistatic properties.

Examples 8 and 9 In the methods of Examples 1 to 4, except that the polymerization time during polyester polymerization was changed so that the molecular weight of the polyester calculated by the end group measurement method was set to about 2.000,
Charge transfer type conjugate 8 synthesized by the same method as Examples 1 to 4
Table 2 shows the properties of the laminated film obtained using Samples and 9.

The laminated films obtained in these Examples also have excellent adhesive properties and antistatic properties.

Comparative Example 1 Examples 1 to 4 were performed except that a polyester having the same composition as Examples 1 to 4 and having a molecular weight of about 20,000 (no introduction of semipolar organic boron bonds and no reaction with an amino compound) was used as the coating liquid. 4
Table 1 shows the properties of the laminated polyester film obtained by the same method as f.

The laminated film obtained in this comparative example has excellent adhesive properties, but is significantly inferior in antistatic properties.

Comparative Example 2 Table 2 shows the properties of polyester films obtained in the same manner as in Examples 1 to 7 except that the coating liquid was not applied.

The polyester film obtained in this comparative example has poor adhesion and antistatic properties.

Margins (Effects of the Invention) The polyester resin composition comprising a charge transfer type bond obtained by the reaction of the semipolar organic boron-bonded gold-plated polyester of the present invention with an amino compound is excellent in printing inks and various coating agents. It has the property of being able to impart strong adhesive properties, and has excellent properties not found in conventional antistatic agents.

Therefore, it is possible to remove the static charge exhibited by insulating materials such as films, sheets, fibers, molded bodies, paper, and their composites, and transform them into materials that do not cause static electricity damage, making them useful in a wide range of fields. can.

In addition, the thermoplastic resin film laminated with the polyester resin composition has both properties of easy adhesion with printing inks and various coating agents and antistatic properties, and antistatic properties are only achieved on one side. It has an extremely interesting property in that even when laminated, antistatic properties are imparted not only to the laminated surface but also to the anti-laminated surface.

Therefore, the laminated thermoplastic film can be suitably used in a wide range of applications such as various packaging applications, plate making applications, magnetic recording applications, and optical applications.

Claims (1)

[Scope of Claims] 1) A semipolar organoboron bond-containing polyester consisting of the following repeating units (I) and/or (II), in which some or all of the semipolar organoboron bonds have reacted with an amino compound for charge transfer. A polyester resin composition comprising a type bond. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1 and R_2 have molecular weights of 300 to 1000.
0 polyester residue) 2) A laminated film obtained by laminating the polyester resin composition according to claim 1 on at least one side of a base film made of a thermoplastic resin.