JPS60242053A - Composite film for thermal lamination - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention A9 Technical Field of the Invention The present invention consists of a saponified ethylene-vinyl acetate copolymer layer with a specific composition and two specific types of adhesive layers, and has blocking resistance with a specific configuration. The present invention also relates to a composite film for thermal lamination that has excellent adhesive properties and has no problems in nulling properties and can be suitably put to practical use.

B. Prior art and its problems Conventionally used films or sheets of plasticized polyvinyl chloride, which is generally referred to as flexible polyvinyl chloride, have an industrial content of 1.25% by weight or more, often 30% by weight.
(Usually, a large amount of plasticizer (more than % by weight) is blended), and therefore, although the sheet etc. is widely used to take advantage of its favorable properties, the plasticizer migrates to the surface. It has a major disadvantage of oozing, and a coating material is being sought that can cover the surface and eliminate this disadvantage.

When soft PVC μ sheets are used for desk mats or document holders, for example, if they come into contact with documents copied by an electrostatic copying machine, printing ink will adhere to the soft PVC sheets within a very short time. There are problems in that the document is damaged and the soft vinyl chloride sheet becomes contaminated, making it impossible to read characters on the printed surface through the sheet. Furniture, office fixtures, etc. made of or covered with printed PVC leather made of soft polyvinyl chloride, as well as wallpaper made essentially of soft polyvinyl chloride, etc. There is a problem that must be solved in that the plasticizer is easily contaminated due to migration and exudation onto the surface, and furthermore, the stain is difficult to wipe off. Furthermore, soft polyvinyl chloride films or sheets are suitable for use in agricultural greenhouses, tunnels, and mulch-only greenhouse horticulture due to their superior heat retention properties compared to polyolefin films or sheets. However, when used for a relatively long period of time, the plasticizer migrates to the surface and oozes out, resulting in staining, which tends to reduce the light transmittance9, and a similar technical problem exists here as well. There have been many attempts to improve this drawback, but none has yet been found that achieves the objective and is satisfactorily put to practical use. The reality is that films or sheets are long-awaited.

On the other hand, there have been attempts to eliminate this drawback by laminating other thermoplastic films onto the flexible polyvinyl chloride film or sheet. Practical coating films include acrylic/l' which can be easily adhered to a film or sheet substantially made of soft polyvinyl chloride by thermal lamination to form a coating layer without using an adhesive. There are resin films. However, the effect of preventing plasticizer migration and oozing is practically not observed.

Other thermoplastics can be used without the use of adhesives, such as thermal lamination, which is the easiest to use, is easily accepted by the polyvinyl chloride film or sheet manufacturer, and is technically the most simple and easily adopted. The coating cannot be applied by adhering to a flexible polyvinyl chloride film or sheet by the adhesive method. Under these circumstances, as with the acrylic resin, the coating can be applied immediately by the thermal lamination method with good adhesive strength without the need for the manufacturer to apply an adhesive. It also prevents the migration and leaching of plasticizers to the surface.
/ Yon film is strongly recommended.

C1 Structure, purpose, and effect of the present invention The present inventors have investigated the plasticizer resistance of various thermoplastic resins, the plasticizers, migration, and We have carried out extensive studies on the leaching properties and staining properties based on external factors, and the ability to clean the stains, and we have developed a material that does not migrate to the surface of the plasticizer and has excellent stain resistance.
We have found a material that can be applied to a plasticized polyvinyl chloride sheet or film by providing it as a coating layer on at least one surface. Furthermore, a multi-layered adhesive that exhibits good adhesion to the material and a different adhesive from the above that exhibits good adhesion to plasticized polyvinyl chloride film, etc., is used, and the latter layer is provided with a specific thickness. By adopting a structure in which the former adhesive layer is adjacent to the material, two types of adhesives can be obtained that do not exhibit blocking properties, have no problems with slip properties, and can be thermally laminated. The present invention has been completed.

The present invention comprises a saponified ethylene-vinyl acetate copolymer layer (5) with an ethylene content of 20 to 60 mol% and a degree of saponification of the vinyl acetate component of 95% or more, 1 m of a reactive polyurethane polymer containing isocyanate groups (B+ and 60 to 99 mol% of vinyl chloride component and vinyl acetate and/or (
It has a vinyl chloride/l'-based copolymer layer fcl containing 40 to 1 mo/l'% of meth)acrylic acid ester component,
The present invention aims to provide a composite film for thermal lamination having a B/C configuration.

09 Detailed Description of the Present Invention The saponified ethylene-vinyl acetate copolymer (hereinafter referred to as EVOH) used in the present invention has an ethylene content of 95% or more. Applicable for polyvinyl chloride.Plasticizers that are liquid at room temperature include dibutyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diisodecyl phthalate, didecyl phthalate, dinonyl tucrate, and schifthalate, which have a melting point of 20°C or less. Phthalate plasticizers such as uryl phthalate, butyl lauryl fugalate, butyl benzyl phthalate, phosphate plasticizers such as tricresyl phosphate, trictyl fonuphat, tri-2-ethylhexyl phosphate, chlorinated/<
There are chlorine-containing plasticizers such as fluorine, and plasticizers that are solid at room temperature, such as dicyclohexyl phthalate, phthalate plasticizers such as heptathalic acid diester with an alcohol order prime number of 13 or more, dipentaerythritol fatty acid ester, etc. polyhydric alcohol plasticizers, trimellitic acid plasticizers such as trioctyl trimellitate, etc.

Ethylene content is 60 mol% or less with respect to these things,
EVOH with a saponification degree of 95% or more exhibits plasticizer resistance and plasticizer migration/exudation resistance.

Among these plasticizers, the former is a plasticizer with particularly remarkable migration-exudation properties, but the EVOH exhibits this effect, and in particular, EVOH with an ethylene content of 55 mol% or less, preferably 50 mol% or less has very satisfactory properties and exhibits virtually no plasticizer permeability.

As the ethylene content increases, the plasticizer permeability gradually decreases, and when it reaches a region exceeding 60 mol%, soft vinyl chloride l
When laminated to a receipt or film, the stain resistance is also reduced as plasticizer leaching onto the surface is gradually observed. On the other hand, as the ethylene content decreases, properties such as plasticizer permeability improve, but in the region of less than 20 mol%, water resistance is poor, and of course the above-mentioned documents may be used in agricultural films etc. In the case of dusters, wallpapers, etc., when wiping off contamination caused by simple external factors unrelated to plasticizer leaching, for example, with a rag, the surface may swell or be damaged. Not suitable. More preferably, the ethylene content is 257 μ% or more. The EVOH of the present invention has an ethylene content of 20 to
60 mole/l/%, preferably in the range of 25 to 50 mole%;
It may be a blend of seeds or more. EVOH with an ethylene content in the range of 20 to 60 mol% has practically satisfactory water resistance, but on the other hand, it is a hydrophilic polymer capable of retaining equilibrium moisture under the conditions of use, so it does not generate static electricity. I can suppress it, Shizuka W
It is also suitable from this point of view since there is no adhesion of dust due to L air.

Also from this point of view, it is more preferable that the ethylene content is 50 mol% or less. Furthermore, as one of the more excellent embodiments that can further improve plasticizer resistance, IIjt agent migration and exudation properties, and further improve the water resistance of the surface of the film, the EVOH film used in the present invention can be further improved. EVOH layer with high ethylene content and EVO with lower ethylene content
There is a preferred embodiment of a composite structure consisting of an H layer. That is, the composite EVOH film has an EVOH layer with an ethylene content of 20 to 35 mol%, and an EVOH layer with an ethylene content of 40 to 60 mol%.
More preferred is an embodiment in which the former layer, which is superior in plasticizer resistance, etc., is disposed adjacent to the OH layer and adjacent to the adhesive layer. The two-layer structure +7) The EVOH film may be used by laminating the two films of different EVOH, but especially the different 2#1! A composite EVOH having the above-mentioned different properties on the front and back surfaces obtained by co-extruding the EVO) I of the two types of EvOH in a molten state inside or outside the gou using a 2PfjJ die. Films are preferably used. In this case, the two EVs
No adhesive resin is required between the OH layers, which is also preferable.

EVOH has extremely good plasticizer resistance, so it is effective even when it is thin, but when it reaches an extremely thin thickness such as 2μ or less, scratches and other damage are likely to occur. The melt film forming operation is not preferred because it increases the technical difficulty in obtaining a pinhole-free film and increases the number of rejected products. In addition, embossing is often applied due to the need for appearance, suppression of gloss, embossing of patterns, etc. In this case, the thickness of the EVOH layer is preferably at least 5 μm or more. ,. Also E
If the VOH layer exceeds 50μ, it is not only economically disadvantageous, but also affects the properties of the mating material to be heat laminated, such as impairing the properties of soft polyvinyl chloride sheets, for example, reducing flexibility. So it's not desirable. 40μ
The following are most suitable.

The EVOH film may be in an unstretched and unprocessed state, but it is more preferably heat-treated from the viewpoint of dimensional stability, water resistance, etc.

EVOH film has superior embossability compared to other resins, and the film for mature lamination of the present invention is often suitably used after being laminated and then embossed. In such a case, an unstretched EVOH film is more suitable. Further, when higher water resistance is required, it is more preferable to use at least uniaxially stretched material. In this case, the stretching ratio is preferably 1.5 times or more for -axial stretching, and the area stretching ratio for biaxial stretching is 3 times or more, preferably 5 times or more.

The other most important requirement for the composite film for thermal lamination of the present invention is a resin having thermal adhesive properties that is laminated on one side of the EVOH. The resin is EVO
It must exhibit good adhesion to H and also to the base material to be thermally laminated, especially plasticized polyvinyl chloride I, and the coated EVOH film must have good blocking resistance. The composite film has good slip properties and has a long shelf life (5 hours) after being obtained as a film for thermal lamination.
elf 1life. This refers to the allowable period of time when a film can be left at room temperature without deteriorating its performance as a film for thermal lamination. ). The adhesive used in the present invention is a reactive polyurethane polymer tB) containing an isocyanate group and a vinyl chloride/vM copolymer fcl containing 60-1:) v% or more of a vinyl chloride component. Ah,
The layer consisting of the adhesive must be used in a laminated form so that the EVOH layer (5) maintains a thickness of at least 1 μm and has a configuration of A/B/C.

Here, the vinyl chloride copolymer containing 6 omol/l/% or more of a vinyl chloride component includes 70 to 95 mol% of a vinyl chloride component and 30 to 5 mol% of a vinyl acetate and/or (meth)acrylic acid ester component. It is preferable that the In addition, some vinyl acetate and/or (meth)acrylic acid ester components include vinyl acetate components, (meth)acrylic ester (methyl esters, esters, etc.) components, or both of these components. It is preferable to use a vinyl chloride copolymer containing one or both of these components. Those modified with three components can also be used. Among these, those modified with maleic anhydride are more preferred. The preferred content of these third components is 0.1 to 5 mo/l/%. As a solvent for the copolymer, methyl ethyl ketone, ethyl acetate, butyl acetate, etc. are preferably used, and as a diluent, methyl ethyl ketone, toluene, etc. are preferably used.

Reactive polyurethane polymers containing isocyanate groups are polymers that have two or more hydroxyl groups in the molecule, such as polyesters obtained by polycondensing ethylene glycol, propylene glycol, and adipic acid, or polyesters obtained by polycondensing ethylene glycol, propylene glycol, and adipic acid, or polyesters obtained by polycondensing ethylene glycol, propylene glycol, and adipic acid, and polyurethane polymers containing two or more hydroxyl groups in the molecule. A polymer having a hydroxyl group in the molecule obtained by partially saponifying a copolymer is mixed with a compound having two or more incyanate groups in the molecule, for example, 1 mole of 1
．． 6-hexamethylene glycol and 2 moles of 2.4-)
It is obtained by mixing a reaction product with lylene diisocyanate or a reaction product with 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate. Furthermore, a compound having two incyanate groups in the molecule may be used alone. As the solvent for the polymer, ethyl acetate, butyl acetate, methifrethyl ketone, toluene, xylene, and the like, which have no reactivity with isocyanate groups, are preferably used.

When the adhesive C is used alone, that is, when the thermal lamination film has an A/C configuration, the adhesive C is
When the surfaces are in contact with each other, for example, when the film is rolled up or stored until use, it exhibits no blocking properties and has good slip properties, and C is a sheet or sheet consisting essentially of plasticized polyvinyl chloride. film,
It exhibits good thermal adhesion to paper and is suitable, but on the other hand, it has a fatal flaw in that the adhesion between A and C is poor and is not sufficient for practical use.

On the other hand, a film for thermal lamination consisting of A/B in which B is used alone has poor adhesion between A and B, and adhesion to a sheet or film made essentially of transportable polyvinyl chloride, paper, etc. Although it is good and satisfactorily practical, it exhibits remarkable blocking properties when three sides are in contact with side A, for example, when the film is wound up and stored until use, and the slip properties are also poor. There are major obstacles to putting it into practical use.

Adhesive B and Cf: A so that the composition is A/B/C.
However, if the adhesive layer is multi-layered, and the thickness of C is at least 1
μ, preferably 1 to 10 μ<BK& When used in layers, the composite film for thermal fumination of the present invention has excellent blocking resistance, no problem in slip properties, and has a long shelf life. . The thickness of C must be at least 1μ, and if the thickness of CM is too small, it is assumed that the unfavorable characteristics of B extend to C, but the details are not clear, but A
The blocking resistance and slipping property of the composite film having the structure /B/C are not satisfactory.

In order to obtain a practically satisfactory composite film, B
The thickness must be at least 1μ. The thickness of layer B should be between 1 and 1, as it would be economically disadvantageous if it were too loose.
The thickness is preferably 10 μm, and suitably 1 to several μm. There is no particular limit to the thickness of A, but if it is too thin, it will be difficult to coat the entire surface uniformly, and if it is too loose, it will be economically disadvantageous.
．． The thickness is preferably 5 to 10 μm, and suitably 0.5 to several μm.

A composite film with a composition of A/B/C in which the two types of adhesives are used so that the thickness of B is at least 1 μm has a long shelf life, and the shelf life of the composite film is long, and after long-term storage, the plasticized polyvinyl chloride becomes Thermal adhesion to film or sheet, paper, etc., which is of interest, is sufficiently satisfactory for practical use.

To provide the multilayer adhesive layer AK, it is possible to first apply β on one side of the person, dry it, and then apply C on the third side. The coating is performed by any means known per se, such as gravure coating, roll coating, doctor roll coating, doctor knife coat barcode, curtain flow coating, etc.

To heat-laminate the composite coated film, usually 1
It can be suitably carried out at 20 to 160°C. If the temperature is too low, the adhesive strength may not be sufficiently developed, and if the temperature is too high, the condition of the EVOA (A1 surface) may deteriorate, which is not preferable.

As mentioned above, the composite film for thermal lamination of the present invention is most suitably used as a film for thermal lamination to plasticized polyvinyl chloride films or sheets, but it can also be used for interior materials consisting essentially of paper, such as wallpaper. It also has good thermal adhesion to substrates such as paper, and is also used as a covering material for products made essentially of paper, with excellent surface stain resistance, easy cleaning of stains, and EVOI (excellent emponent layer). It can provide processability and can be suitably used.

Next, examples will be described with reference to examples, but the scope of the present invention is not limited thereto.

Example 1 Ethylene content 31 mol%, saponification degree of vinyl acetate component 9
First, the solid content of urethane adhesive AD335 and curing agent Cat-10 (manufactured by Toyo Morton Co., Ltd., mixing ratio 17:1, belonging to B above) was applied to a 15μ thick film of 9.3% EVOH using a gravure coater. A solution of toluene/methyl ethyl ketone = "A (weight ratio) with a concentration of 2oIJli% is zy/
d (based on solid content) and heated at 110°C, 1
After drying for minutes, a maleic anhydride-modified vinyl chloride-vinyl acetate copolymer adhesive MPR-TM
(Manufactured by Nichiken Gakusha. Belongs to the above C. Vinyl chloride/I/(
86 mol%) - acetic acid k''2A/(13 mol%) - maleic anhydride (1 mol/L/%) modified vinyl chloride μ ~ vinyl acetate copolymer.) toluene with a solid concentration of 20% by weight /meflVethy~ketone=V2 (weight ratio) solution at 2 p/
lh (based on solid content) and dried under the same conditions as above. The thicknesses of the B layer and the B layer of the obtained composite film were 2.1μ and 2.0μ, respectively. In order to examine the blocking property of the obtained coated composite film, the uncoated EVOH was added to the zero side of the coated composite film.
It was investigated whether the adhesion after 24 hours of adhesion with a film under a pressure of so Vc& would be a problem in practical use. No adhesion was observed, and it was confirmed that there was no problem with blocking properties. Moreover, the slip property of the coated composite film was also good. 38% by weight of di-2-ethylhexyl phthalate was added to the coated composite film after 50 days.
It was laminated onto the surface of a 0.3 m soft polyvinyl chloride sheet containing the material by thermal lamination at a temperature of 150°C. The adhesive strength was measured by T-peeling, and it was confirmed that the soft polyvinyl chloride layer was destroyed and had sufficient adhesive strength. A non-plastic hard polyvinyl chloride plate (6α x 6 CM, thickness 2 mm) is placed in close contact with the EVOH side of the soft polyvinyl chloride sheet on which the above composite film is laminated, and a weight of 2 kg is placed on the hard vinyl chloride plate. The amount of exudation and transfer of the plasticizer was investigated at a temperature of 70° C. under a load of 70° C. Even after 50 hours had elapsed, no sudden increase in the hardness of the hard polyvinyl chloride board was observed, nor was there any stickiness on the EvOH surface, indicating that migration and oozing of the plasticizer was completely prevented. 1)'t or MP R-T by wiping with a wet cloth
Using M, a coated film having the above-mentioned A/B or A/C structure was obtained in the same manner as above.

The coated eye film having the structure A/B had significant blocking properties and poor slip properties, making it difficult to use as a film for thermal lamination.

In addition, the coated film with A/C structure has blocking properties,
Although the slip property was satisfactory, the adhesion strength was examined after the soft polyvinyl chloride sheet was laminated, but A
, C was 0.28 kg725 m, which was insufficient for practical use.

For comparison, a soil layer of an acrylic copolymer containing 86 mol% of methyl methacrylate and 14 mol% of butylene methacrylate and having the same thickness as the EVOH was heated on the soft polyvinyl chloride sheet. The laminated sheets were similarly tested. The change in gravity of the hard polyvinyl chloride board after 24 hours was 3.2% by weight. It was confirmed that the weight change was caused by the transfer of the plasticizer, and stickiness on the surface of the copolymer film was also observed.

Example 2 Using an EVOH film with an ethylene content of 43 mol% and a saponification degree of vinyl acetate component of 99.3 mol% in Example 1, the coated composite film was obtained and thermal lamination was performed at a temperature of 130°C. The procedure of Example IK was followed except for the following, and the exudation migration test, blocking property test, etc. of the plasticizer were conducted. However, the coating amount of adhesive C was about 1.2μ, and as a result, the thickness of the C layer was 1.1μ.

The coated composite film exhibited good anti-blocking properties and good slip properties, and no change in the weight of the hard polyvinyl chloride plate was observed. When the core interlayer adhesion force was measured by T-layer peeling, the soft polyvinyl chloride layer was destroyed. The water resistance of the EVOH surface was also sufficient.

Example 3 gvoHfX) with ethylene content of 1t26 mol% and saponification degree of vinyl acetate component of 99.5 mo/I/%) and ethylene content of 5
EVOH (Y) with a saponification degree of 1 mol % and vinyl acetate component of 99.3 mol % was supplied to two extruders, and a two-shoe T-
The molten resins were bonded in a die at 220° C. using a die to obtain a composite EVOH film in which the EvoaiXI layer had a thickness of 6 μm and the EVOHfY layer had a thickness of 9 μm. The composite EV
Heat lamination was performed according to Example 1 so that the X side of the OH film was adjacent to the soft polyvinyl chloride via a multilayer adhesive, and the film was subjected to various tests.

However, the adhesive used is urethane adhesive EP8-703 and curing agent KP-90 (manufactured by Dainippon Ink Co., Ltd., mixing ratio 15:1).
゜1,) belonging to B above and EPR-T used in Example 1
As a result, the thickness of the can adhesive layer was 8 layers, 369μ, and the C' layer, 3.
The composite film was xμ. In addition, as a plasticizer for the soft polyvinyl chloride sheet, di-n-octyl phthalate/tri-2-ethylhexyl phosphate) = 5
Thermal lamination was performed at a temperature of 125° C. using a flexible polyvinyl chloride sheet containing 35% by weight of a mixture of 0150 (weight ratio).

The obtained coated composite film exhibited good anti-blocking properties and also had good slip properties.

The flexible polyvinyl chloride sheet laminated with the composite film was examined in the same manner as in Example 1 to see if there was any leaching or transfer of the plasticizer, and as a result, neither the weight change nor the surface stickiness was observed. The adhesive strength of the polyvinyl chloride layer was also insufficient, and when the adhesive strength was measured by peeling off the T layer, the polyvinyl chloride layer was destroyed.

For comparison, the acrylic copolymer film used in Example 1 was thermally laminated onto the flexible polyvinyl chloride sheet, and the resulting multilayer sheet was examined to see if the plasticizer oozed out or migrated. The weight increase of the hard PVC board was 3.1 after 30 hours.
% by weight.

For comparison, EPS-703 and curing agent were used as adhesives.
Coat EVO consisting of A/B configuration using KP-90
) A film was obtained, but both blocking properties and slip properties were poor and it could not be used as a film for thermal lamination.

Example 4 In Example 1, biaxial stretching with ethylene content of 49 mol% and saponification i of vinyl acetate component of 99.2% (area stretching ratio 3
x3 times) EVOH film is used, and a plasticizer chlorinated paraffin/di-vinyl chloride sheet is used as a soft polyvinyl chloride sheet.
The sheet containing 42% by weight of a mixture of n-octyl phthalate = 50150 (weight ratio) was used as a urethane adhesive with AD-900 and curing agent AD-RT5 (manufactured by Toyo Morton Co., Ltd., mixing ratio 100:15o, which belongs to the above B). ) was used in the same manner as in Example 1. Both the blocking resistance and the slipping property of the TO 1-composite film were good, and neither heavy electrical changes in the hard vinyl chloride plate nor oozing of the plasticizer onto the EVOH surface was observed. The adhesive strength between the layers was also sufficient, and when the adhesive strength was measured by peeling off the T layer,
The polyvinyl chloride layer was destroyed. The water resistance of the EVOH surface was also sufficient.

In the case of a film made of the same acrylic copolymer as in Example 1 used for comparison, the weight change was 3.1% by weight, and stickiness on the surface of the film was also observed.

Also, for comparison, AD-900 and hardened j'r! I.A.D.
A coated film consisting of composition A/B using only urethane adhesive of -1ζT5 was obtained according to the above method, but although the interlayer adhesion was sufficient as the polyvinyl chloride layer was destroyed, the coated film The locking and slipping properties of the film were extremely unsatisfactory, and it was not put to practical use.

Example 5 In Example 1, as the urethane adhesive, a mixture of tolylene diisocyanate (Coronate L1 manufactured by Nippon Polyurethane Industries, Ltd.) and polyene ether with a glycol terminal having a molecular weight of about SOO (mixing ratio (weight) 1:2) was used. was carried out in the same manner as in Example 1.

The coated composite film had good anti-blocking properties and good nulling properties. Furthermore, no change in weight of the hard polyvinyl chloride board was observed. Further, the interlayer adhesive strength was insufficient, and when the adhesive strength was measured by T-peel, the soft polyvinyl chloride layer was destroyed.

Patent applicant RiRashi Co., Ltd. Agent: Patent Attorney Ken Honda procedural correction officer October 26, 1980 Mr. Manabu Shiga, Commissioner of the Patent Office ■Display of incident Special Application No. 59-9945 2. Name of the invention Composite film for thermal lamination 3. Person who makes corrections Relationship to the incident: Patent applicant 1621 Sakazu, Kurashiki City (I O8) RiRashi Co., Ltd. Representative Director Iya Kamino − 4th generation manager Kurashiki City Alcoholic Disorder Aoeyama 2045-1 Claims column of the specification and 6. Contents of amendment (1) Amend the claims as shown in the attached sheet.

(2) Question #B, page 19, lines 3 to 4, [Plasticized polyvinyl chloride film or sheet J] is a plasticized polyvinyl chloride film containing 25 to 55% by weight of the above-mentioned plasticizer based on the total weight. ``Plasticized polyvinyl tetrachloride film or sheet''.

Claims (1) A saponified ethylene-vinyl acetate copolymer layer containing 20 to 60 mol% of ethylene a, a degree of saponification of the vinyl acetate component of 95% or more +A+, and a reactive polyurethane-based polymer layer fBl containing isocyanate groups. and vinyl chloride component from 60 to
For thermal lamination, having a vinyl chloride copolymer layer tc) containing 99 mol% and 40 to 1 mol% of vinyl acetate and/or (meth)acrylic acid ester components, and consisting of A/B/C configuration. Image matching film.

(2) The composite film according to claim 1, wherein the ethylene content is 25 to 50% by volume.

(3) Thickness of A is 2-50μ, thickness of B is 05-10μ
and C has a thickness of 1 to 10μ.
Or the composite film according to any one of Item 2.

(4) A patent claim in which A consists of two layers: the saponified layer having an ethylene content of 20 to 35 mol% and the saponified layer having an ethylene content of 40 to 60 mol%, and the former is adjacent to B. The composite film according to any one of items 1 to 3.

(5) A film made essentially of plasticized polyvinyl chloride! The composite film according to any one of claims 1 to 4, which is used for thermal lamination to an FCU sheet.

Patent Office Multi-Official Uga Michibu 1 Case Display Patent Application No. 59-99452 2 Name of Invention Composite Film for Thermal Lamination 3 Person Who Makes Amendments Relationship with the Case Patent Applicant Kurashiki City Sake/J1621 (l 08) ) RiRa Co., Ltd. 2045-1 Aoeyama, Sakazu, Kurashiki City Kuraray Co., Ltd. Patent Department 6, Self-answer of amendment (1) “Adhesive layer and Shikamon” in line 1 of page 17 of the specification
is corrected to ``use an adhesive layer, and also''.

(2) Delete "Practically satisfactory...appropriate." from lines 13 to 17 on page 17.

(3) Correct "methyl ester, ester J" on page 14, line 9 of the same page to "methyl ester, ethyl ester".

(4) "Correct AJ to "B" on page 17, line 17.

(5) “1 and B” on page 18, line 3 [and CJ
and correct it.

(6) On page 20, line 4 of the same, "MPR-TM (Nichisei Chemical)" is corrected to "MPR-TM (8 Shin Kagaku)".

(7) "Combined.)" on page 20, line 8 of the same page is combined. )”
and correct it.

(8) On page 20, line 20, 1 and layer ko are corrected to read "and layer 6."

(9) Page 21, lines 3 to 4 [Laminated at a temperature of 150° C. by thermal lamination method. '' was laminated by one heat lamination method (using a roll at 150° C.). ” he corrected.

(10, page 23, bottom line, "Multiple layers of one adhesive" is corrected to "Multiple layers of adhesive."

(6) On page 24, line 5, the (-) and Example 1 are corrected to "[)Methyl ethyl keto/Solution and Example]".

04 r EPS-703J on page 25, line 7
Correct with EPS-703AJ.

03 Insert the following information between lines 12 and 13 on page 27 of the same document.

Example 6 Except for using a copolymer of 80 mol% vinyl chloride component, 17 mol% vinyl acetate component, and 3 mol% ethyl acrylate component as the vinyl chloride adhesive (C) in Example 1.
The film for thermal lamination/i obtained in the same manner as in Example 1 exhibited good blocking resistance and also had good slip properties. It was laminated on the surface of a soft vinyl chloride sheet in the same manner as the thermal lamination film LA*AI. T
Adhesive strength was measured by peeling off the mold, and it was confirmed that the soft vinyl chloride layer was destroyed and had sufficient adhesion. ”

Claims (6)

[Claims] (1) A saponified ethylene-vinyl acetate copolymer layer with an ethylene content of 20 to 60 mol% and a saponification degree of 95% or more of the acetic acid H=/' component (5) A reactive polyurethane polymer layer containing isocyanate groups ( 60% of Bl and vinyl chloride components
~99 mol% and vinyl acetate and/or (meth)
A composite film for thermal lamination having a vinyl chloride copolymer layer fcl containing 40 to 1 mol% of an acrylic acid ester component and having an A/B/C configuration. (2) The composite film 7rem according to claim 1, having an ethylene content of 25 to 50 mo/l/%. (3) The thickness of the person is 2 to 50 μ, the thickness of B is 0.5 to 10
The composite film according to claim 1 or 2, wherein the thicknesses of μ and C are 1 to 10 μ. (4) A is two of the saponified layer having an ethylene content of 20 to 35 mol% and the saponified layer having an ethylene content of 40 to 60 mol%.
4. A composite film according to any one of claims 1 to 3, wherein the composite film has no layers and the former is adjacent to B. (5) The composite film according to any one of claims 1 to 4, which is used for thermal lamination to a film or sheet consisting essentially of plasticized polyvinyl chloride. (6) Claims 1 to 4 are for thermal lamination of a film or sheet consisting essentially of plasticized polyvinyl chloride containing 25 to 70% by weight of a plasticizer that is liquid at 20°C. The composite film according to any one of.