JPS63268641A - Thermoplastic resin film laminate - Google Patents

Abstract

PURPOSE:To make smoothness and sliding characteristics good, by laminating a polyester resin composition prepared by compounding a specific water-insoluble polyester copolymer and a compound selected from partially hydrolyzed alkyl silicates, organic silane compounds and organic titanates at a specific wt. ratio on one surface. CONSTITUTION:Polyester copolymer (A) is a substantially water-insoluble polyester copolymer obtained by reacting a mixed dicarboxylic acid consisting of 0.5-15mol.% of dicarboxylic acid containing a metal sulfonate group and 85-99.5mol.% of dicarboxylic acid containing no metal sulfonate, with a glycol component. A polyester resin composition is obtained by compounding the polyester copolymer (A) and a compound (B) selected from partially hydrolyzed alkyl silicates, organic silane compounds and organic titanates. The wt. ratio of compounding is preferably (A)/(B)=100,000/5-100,000/50,000, and more preferably (A)/(B)=1,000/2-1,000/200.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermoplastic resin film laminate with excellent slipperiness and smoothness.

(Prior Art) As is well known, thermoplastic resin films, such as polyester, polyamide, polypropylene, etc., especially polyester films, especially polyethylene terephthalate films, have a high degree of crystallinity, excellent transparent gloss, mechanical properties, chemical resistance, and heat resistance. It is rapidly being used for a wide range of purposes year by year.

However, as is known from the past, if the coefficient of friction of a polyester film is large, the films will not slide against each other, and if it is extremely poor, blocking will occur, making it difficult not only to handle the film but also to make it particularly difficult to wind it up. Conventionally, this objective has been achieved by adding inorganic or organic substances alone or in combination to the film in order to lower the coefficient of friction of the film.However, if the amount added to such a film is small, the Since the effect is small and a large amount is added, the transparency of the film rapidly decreases.In other words, there is no film that has almost the same transparency as a film without additives and a significant reduction in the friction coefficient of the film. Furthermore, even if the same amount of the same additive is added to polyester, the rate of decrease in the coefficient of friction largely depends on the heat treatment conditions, and the greater the thermal history, the greater the rate of decrease.On the other hand, A method has been proposed to obtain a film with excellent lubricity and transparency by adding polyorganosiloxane or the like to a polyester film. The decrease in transparency is not noticeable, and mechanical properties such as dimensional stability and Young's modulus also tend to decrease.Furthermore, there is a method of applying knurl processing before winding, but the knurled part is removed by slitting in secondary processing. Conventional manufacturing methods have had various problems, such as being trimmed or being present only on one side.

(Problems to be Solved by the Invention) As a result of the present inventors' intensive research and efforts to solve the problems in the conventional techniques, namely the difficulty of imparting smoothness and slipperiness at the same time, the present invention has been developed. This is what we have come to complete.

(Means for Solving the Problems) That is, the present invention provides (A) a total dicarboxylic acid component of 0.5 to
A water-insoluble polyester copolymer formed from a glycol component and a mixed dicarboxylic acid component containing 15 mol% of a sulfonic acid metal group-containing dicarboxylic acid, and (B) an alkyl silicate partial hydrolyzate, an organosilane compound, and an organotitanate. At least one compound selected from (A)/(B) = 10000015 to 100
This is a thermoplastic resin film laminate characterized in that a polyester resin composition blended at a weight ratio of 000150,000 is laminated on at least one side.

The polyester copolymer (A) of the present invention comprises 0.5 to 15 mol% of a dicarboxylic acid containing a sulfonic acid metal group and 85 to 99.5 mol% of a dicarboxylic acid containing no sulfonic acid metal group.
It is a substantially water-insoluble polyester copolymer obtained by reacting a glycol component with a dicarboxylic acid mixed with mol%. Substantially water-insoluble means that the polyester copolymer does not dissipate in hot water even if the polyester copolymer is stirred in hot water at 80°C. The weight loss of the polyester copolymer after being stirred in excess 80'C hot water for 24 hours is 5% by weight or less.

The above-mentioned sulfonic acid metal base-containing dicarboxylic acids include:
Examples include metal salts of sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5(4-sulfophenoxy]isophthalic acid, with 5-sulfophthalic acid being particularly preferred. These are sodium sulfoisophthalic acid and sodium sulfoterephthalic acid.These sulfonic acid metal base-containing dicarboxylic acid components are 0.5 to 15 mol% of the total dicarboxylic acid components, and if it exceeds 15 mol%, polyester copolymerization The water resistance of the combined product is significantly reduced, and if 0.5 mol % is left ungrooved, the dispersibility of particles formed from partial hydrolysates of alkyl silicate, organic silane compounds, and organic titanates is significantly reduced.

Dicarboxylic acids that do not contain sulfonic acid metal bases include:
Aromatic, aliphatic, and alicyclic dicarboxylic acids can be used.

Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid. These aromatic dicarboxylic acids preferably account for 40 mol% or more of the total dicarboxylic acid components. If the amount is less than 40 mol%, the mechanical strength and water resistance of the polyester copolymer will decrease. Aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, 1,3-cyclopentanedicarboxylic acid, 1.2
-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Addition of these non-aromatic dicarboxylic acid components may improve adhesive performance in some cases, but generally reduces the mechanical strength and water resistance of the polyester copolymer.

The glycol component to be reacted with the mixed dicarboxylic acid is an aliphatic glycol having 2 to 8 carbon atoms or an alicyclic glycol having 6 to 12 carbon atoms, and specifically, ethylene glycol, 1,2-propylene glycol, j
, 3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1
．． These include 2-cyclohexane dimetatool, 1,3-cyclohexane dimetatool, 1,4-cyclohexane dimetatool, p-xylylene glycol, diethylene glycol, triethylene glycol, and the like. Further, examples of the polyether include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

Polyester copolymers are obtained by conventional melt polycondensation. In other words, there is a direct esterification method in which the above dicarboxylic acid component and glycol component are directly reacted, water is distilled off and esterified, and then polycondensation is performed, or the dimethyl ester of the above dicarboxylic acid component and the glycol component are reacted to form methyl alcohol. It can be obtained by a transesterification method, etc., which involves distilling off, transesterifying, and then polycondensing it. In addition, solution polycondensation, interfacial polycondensation, etc. may also be used, and the polyester copolymer of the present invention is not limited by the polycondensation method.

When laminating on a film a polyester resin composition containing at least one compound selected from the above polyester copolymer and a partial hydrolyzate of an alkyl silicate, an organic silane compound, and an organic titanate, the polyester copolymer and A method of simultaneously coextruding the film and raw material resin from separate extrusion ports of an extruder, a method of extruding and laminating a molten sheet of the polyester copolymer onto a film, a partial hydrolyzate of alkyl silicate, an organic silane compound, There are methods of coating a film with an aqueous dispersion of the polyester copolymer blended with at least one compound selected from organic titanates, and any method may be adopted; A method of coating a dispersion liquid is more preferable in terms of ease of slipping since a thin film can be formed on the film.

In order to obtain an aqueous dispersion of the polyester copolymer, it is necessary to disperse it in water together with a water-soluble organic compound. For example, the polyester copolymer and the water-soluble organic compound are mixed in advance at 50 to 200°C, and water is added to this mixture and dispersed by stirring, or conversely, the mixture is added to water and dispersed by stirring. Alternatively, there is a method in which a polyester copolymer, a water-soluble organic compound, and water are made to coexist and stirred at 40 to 120°C.

The above-mentioned water-soluble organic compound is an organic compound having a solubility in water of 20 g or more at 20°C, and specifically includes aliphatic and alicyclic alcohols, ethers, esters, and ketone compounds, such as methanol and ethanol. , Impropatol, iar alcohols such as n-butanol, glycols such as ethylene glycol and propylene glycol, methyl cellosolve, ethyl cellosolve, n-
Glycol derivatives such as butyl cellosolve, dioxane,
These include ethers such as tetrahydrofuran, esters such as ethyl acetate, and ketones such as methyl ethyl ketone. These water-soluble organic compounds can be used alone or in combination of two or more. Among the above compounds, butyl cellosolve and ethyl cellosolve are preferred in terms of dispersibility in water and coatability on films.

The weight ratio of (A) polyester copolymer, (C) water-soluble organic compound, and (D) water is (A)/(C).
= 100/20~10015000(C)/(D)=
It is important to titrate from 100150 to 100/10000. When the amount of the water-soluble organic compound is small relative to the polyester copolymer and the ratio (A)/(C) exceeds 100/20, the dispersibility of the aqueous dispersion decreases. In this case, dispersibility can be assisted by adding a surfactant, but if the amount of surfactant is too large, the attachment property and water resistance will be reduced. Conversely, (A)/(C') is 1001
5000 less tR17), Mataha (C)/(D) Ka1
If it exceeds 0 o 15 o, the amount of water-soluble organic compounds in the aqueous dispersion increases and there is a risk of solvent remaining after coating. Furthermore, the cost will be higher, so consider recovering the compound.
,! 5 Necessary bi Al, (C) / (D) Ka10
If the 0/10000 groove is not formed, the surface tension of the aqueous dispersion increases, the wettability to the film decreases, and coating spots are likely to occur. In this case, the wettability can be improved by adding a surfactant, but if the amount of the surfactant is too large, the attachability and water resistance decrease as described above.

Furthermore, the partial hydrolyzate of alkyl silicate (B) to be added to this dispersion includes partial hydrolyzates such as methyl silicate, ethyl silicate, n-propyl silicate, n-butyl silicate, and isoamyl silicate. These hydrolyses are carried out by adding water in the presence of an alcohol such as ethyl alcohol. Although the hydrolysis rate can be changed arbitrarily, a completely hydrolyzed product is not preferred before addition due to its affinity with water-insoluble polyester. In addition, (B) organic silane compounds include tetraisoprooxysilane and polymers, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane,
γ-methacryloxypropyltrimethoxysilane, γ-
Methacryloxyproplutris(β-methoxyethoxy)silane, β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-
Mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β(aminoethyl)-
Examples include, but are not limited to, γ-aminopropylmethoxysilane.

(B) Organic titanates include tetra-n-butoxy titanium and polymers, tetrakis(2-ethylhexyl) titanium, diisoprooxybis(acetylacetonato)titanium, di-n-butoxybis(triethanolaminate)titanium, dihydroxybis( silicate) titanium and its salts, titanium isopropoxyoctylene glycolate, (ethylene glycolade) titanium bis(dioctyl fuomafuate), oxotitane bis(ammonium oxalate), tri-n-butoxytitanium monostearate, impropoxytitanium disilicate Methacrylate isostearate, isopropoxy titanium tris(
4-aminobenzoate), but are not limited to these. Preferably dihydroxybis(
silicate) titanium and its salts and oxotitane bis(
monoammonium oxalate), dibutoxybis(triethanolaminate)titanium, and impropoxytitanium triisostearate.

The amount of (B) used for (A) is (A)/(B) = 1
The ratio of 0000015 to 100000150000 is good, preferably (A)/(B) = 1000/2 to 10
It is 00/200.

In addition to the alkyl silicate hydrolyzate, the aqueous dispersion of the polyester copolymer thus obtained contains inorganic or organic crosslinking agents, inert particles, lubricants, colorants, antistatic agents, etc.
Additives such as a conductive agent, a surfactant, and a leveling agent may be mixed. Furthermore, polymers such as acrylic, urethane, epoxy, polyamide, rubber, cellulose, and vinyl ester may be mixed.

The aqueous dispersion of the polyester copolymer obtained in this manner may be applied to a polyester film by a coating method, either on an unstretched film obtained by melt-extruding the polyester film, or on an axially stretched film or a two-wheel stretched film. However, since the film is wide and the film travels at a high speed when coating stretched film on two wheels, it is difficult to apply the film evenly. It is more preferable in these respects.

The amount of the aqueous dispersion applied to the polyester film by the coating method is 0.01 to 5.0 g/polyester copolymer as the amount present on the film after two-wheel stretching.
/ is. The application amount is 0.01g//If the groove is not grooved, the adhesion force is weak (and the durability is poor.5.0g/II)
If more than P is applied, the slipperiness will worsen.

In addition, by subjecting the polyester film to a corona discharge treatment before applying the aqueous dispersion of the polyester copolymer, the coating properties of the aqueous dispersion are improved and the bond between the polyester film and the polyester copolymer coating film is improved. The adhesive strength between the two is improved. In addition, the wettability of the film surface and the bondability can be improved by subjecting the polyester copolymer material after coating or two-wheel stretching to corona discharge treatment, corona discharge treatment under a nitrogen atmosphere, ultraviolet irradiation treatment, etc. be able to.

Further, in the present invention, it is preferable to use a polyester film, especially a polyethylene terephthalate film, as the thermoplastic resin film because 1[ and film waste generated in the film forming process etc. can be collected and reused.

In addition, in terms of smoothness, it is preferable for the polyester to contain as little lubricant m as possible, preferably 300 pp-
It is as follows. However, in order to obtain high slipperiness and smoothness, 3
00 ppm or more may be sufficient.

The coated polyester film produced by the above method can be applied to magnetic tape base films, lapel sticker base films, chemical mat base films, overhead projector films, food packaging films, and all other applications where polyester films are used. It can be used for any purpose.

(Example) The present invention will be described in detail below. In the middle part of the example, percentages are based on weight.

The measurement method adopted in the examples is as follows.

(1) Friction coefficient This is a value measured on both the laminated surface and the non-laminated surface using Tensilon manufactured by Toyo Seiki Co., Ltd. in accordance with ASTM-1894.

■ Surface smoothness of the film Using a Surfcom 300A surface roughness meter (manufactured by Tokyo Seimitsu), the needle diameter was 1 μm, the weight was 0, and the measurement standard length was 0.7 g s.
It is expressed as center line average roughness RA (μ-)) measured under the conditions of 8+n, cutoff O, and OS Tsuru.

Example l.

(1) Production of polyethylene terephthalate Ethylene glycol 200m lead hydroxide pbO-pb (OH
), 2.2 g (pbo, 95X10''%) 11
10-' mol) was added and heated under reflux at the boiling point of ethylene glycol at 197°C, a clear solution was obtained in about 30 minutes.

Next, polyethylene terephthalate was produced using this solution as a polycondensation catalyst. dimethyl terephthalate) 82
0 parts, ethylene glycol 4808B, and zinc acetate Z n (OAC) m2H2O as a transesterification catalyst were reacted, and polycondensation reaction was further performed for 2 hours under reduced pressure (11 g of 10 to 0.2 g) to give an average molecular weight of 18,000 and softening. Point 1
A polyester copolymer at 40°C was obtained.

300 parts of this polyester copolymer and 140 parts of n-butyl cellosolve were stirred in a container at 150 to 170°C for about 3 hours to obtain a homogeneous and viscous melt.
After about 1 hour, 580 parts of water was gradually added to the solution to obtain a homogeneous pale white aqueous dispersion with a solid content concentration of 30%, and to this was further added a decomposition product of ethyl silicate with a hydrolysis rate of 50% based on the above solid content. 2.5% by weight was added and mixed under stirring while applying ultrasonic waves, and diluted by adding 1500 R of water and 1500 parts of ethyl alcohol to obtain a coating liquid with a solid content concentration of 8%. This solution was left at 40'C for 48 hours and used in the next step.

■ 280% polyethylene terephthalate produced in production of coated film (1)
The unstretched film was melt-extruded at ~300'C and cooled with a cooling roll at 15°C to obtain an unstretched film with a thickness of 1000 microns. Stretched 5 times, applied the above coating solution using an air knife method, dried with hot air at 70°C, then stretched 3.5 times in the transverse direction at 98°C with a tenter, and further stretched 200 to 200°C.
A two-wheel stretch coated polyester film having a thickness of 100 microns was obtained by heat setting at 10'C.

The physical properties of the obtained film are shown in Table 1. As can be seen from Table 1, the obtained film has excellent slipperiness and smoothness.

Example 2 A film was obtained in the same manner as in Example 1 except that propyl silicate was used instead of ethyl silicate.

The physical properties of the obtained film are shown in Table 1. As can be seen from Table 1, the obtained film has excellent slipperiness and smoothness.

Comparative Example 1゜A film was obtained in the same manner as in Example 1 except that ethyl silicate was not added.

The physical properties of the obtained film are shown in Table 1. No.

As can be seen from Table 1, the obtained film was smooth but had poor slipperiness.

Comparative Example 2 A film was obtained in the same manner as in Example 1 except that no coating was applied in Example 1.

The physical properties of the obtained film are shown in Table 1. As can be seen from Table 1, the obtained film was smooth but had poor slipperiness.

Table 1 Examples & Example 1 A polyester film was obtained in the same manner as in Example 1, except that 2.5% by weight of vinyl ethoxysilane was added instead of ethyl silicate.

The physical properties of the obtained film are shown in Table 2. As can be seen from Table 2, the obtained film has excellent slipperiness and smoothness.

Example Tun A film was obtained in the same manner as in Example 1 except that vinyl ethoxysilane in Example 3 was changed to vinylchlorosilane.

The physical properties of the obtained film are shown in Table 2. As can be seen from Table 2, the obtained film has excellent slipperiness and smoothness.

Comparative Example & Example 3 A film was obtained in the same manner as in Example 3 except that vinyl ethoxysilane was not added.

The physical properties of the obtained film are shown in Table 2. As can be seen from Table 2, the obtained film has excellent slipperiness and smoothness.

Table 2 Example 5゜In the same manner as in Example 1, 2.5 oxatitan bis(monoammonium oxalate) was added instead of ethyl silicate.
A polyester film was obtained in the same manner as in Example 1 except that % by weight was added.

The physical properties of the obtained film are shown in Table 3. As can be seen from Table 3, the obtained film has excellent slipperiness and smoothness.

Examples & A film was obtained in the same manner as in Example 1 except that the organic titanate in Example 1 was changed to di-n-butoxybis(triethanolaminate) titanium.

゛ The physical properties of the obtained film are shown in Table 3. As can be seen from Table 3, the obtained film has excellent slipperiness and smoothness.

Comparative Example A film was obtained in the same manner as in Example 5 except that oxotitane bis(monoammonium oxalate) was not added.

Third, a polyester film was obtained in the same manner as in Example 1 by adding the surfaced material.

Excellent slipperiness and smoothness.

The plastic resin film laminate has the advantage of being smooth and having good slipperiness.

Claims (1)

[Claims] (1) (A) 0.5 to 15 mol% in total dicarboxylic acid components
A water-insoluble polyester copolymer formed from a mixed dicarboxylic acid component containing a sulfonic acid metal group-containing dicarboxylic acid and a glycol component, and (B) a partial hydrolyzate of an alkyl silicate, an organic silane compound, and an organic titanate. At least one selected compound (A)/(B)=100000/5 to 100000/5
1. A thermoplastic resin film laminate, characterized in that a polyester resin composition blended at a weight ratio of 0,000 is laminated on at least one side.