JP5470809B2 - Manufacturing method of laminate - Google Patents

Description

The present invention relates to a method for manufacturing a laminate .

Conventionally, a solventless functional silicone composition has been used so that an adhesive substance does not adhere to or adhere to a substrate such as paper or plastic. These functional silicone compositions have good adhesion to paper, laminated paper and the like, but are insufficient for plastic films such as polyethylene terephthalate and polypropylene films. In particular, when the functional silicone composition is cured at a low temperature to prevent the film from shrinking, there is a problem that the adhesion deteriorates, and the cured silicone film obtained by rubbing with a finger under high humidity conditions There was also a problem of peeling off.
For this reason, it has been proposed to add a certain kind of silane, siloxane or the like to provide self-adhesiveness for the purpose of improving the adhesion to the plastic film for the conventional functional silicone composition. These are all cured using a condensation reaction and require a high temperature for curing, and thus are not suitable for forming a cured silicone film on a plastic film. A composition is also known in which a siloxane containing this epoxy group at the terminal or side chain is used and cured by an addition reaction. However, the non-adhesiveness of the cured film was not satisfactory.

In addition, as a laminate using the functional silicone composition, a film made of an addition-polymerized cured product of a silicone compound having a vinylsiloxane group on at least one side of a polyester film, a condensation-polymerized cured product of an alkyloxysilane or an oxysilane compound, etc. The provided one is used. This cured product has the advantage that it is non-adhesive and has excellent functional effects, but on the other hand, it has a problem that the adhesion with the polyester film as the base film is insufficient and the durability is low.
In addition, the following patent documents 1-7 are illustrated as a prior art.
Japanese Patent Laid-Open No. 50-141591 JP 57-77395 A JP-A-52-24258 JP-A-52-147657 JP-A-1-5838 Japanese Patent Laid-Open No. 6-220327 JP 2004-43625 A

  In order to improve the adhesion between the polyester film and the silicone layer, there is a method of using silicone-modified urethane or acrylic resin as a functional layer, but this method has an essential drawback that the functionality of the functional layer is inferior.

  As a method for improving the adhesion between the silicone layer and the polyester film, a method of providing a crosslinked primer layer of a silane coupling agent has been proposed. However, in this method, it is difficult to control the reactivity of the silane coupling agent, the pot life of the coating liquid is short, it is difficult to form a uniform film, and the productivity is low.

  Furthermore, in order to improve the adhesion to the film substrate, there are improvement methods such as production of a specific silicone composition and production of a dedicated film, but problems such as cost and application range are not solved.

  Accordingly, the present invention provides an anchor coating agent for coating a silicone layer that solves the problems of the prior art and has high transparency to a substrate such as a film, excellent adhesion, and can be cured at low temperature. With the goal. Moreover, it aims at providing the laminated body which is a functional silicone film using the same.

The invention according to claim 1 is, in an organic solvent, (1) tetramethoxylane, tetraethoxylane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, An alkoxysilane selected from 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; and (2) 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 A plastic film-based anchor coating agent for coating comprising an alkoxysilane selected from acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, and a metal chelate Apply on material And that process,
Curing the coating anchor coat agent at a curing temperature of 100 to 200 ° C. and a curing time of 10 to 60 seconds to form an anchor coat layer;
Applying a silicone coating agent on the anchor coating layer to form a silicone layer;
It is a manufacturing method of the laminated body characterized by providing .
Invention of Claim 2 is a manufacturing method of the laminated body of Claim 1 in which the said organic solvent contains both a hydrophilic solvent and a hydrophobic organic solvent.
The invention according to claim 3 is characterized in that the metal chelate has a general formula R ⁴ OH (R ⁴ represents an alkyl group having 1 to 8 carbon atoms) and / or R ⁵ COCH ₂ COR ⁶ (R ⁵ represents a carbon 1 to 1 carbon atom). An alkyl group of 8 and R ⁶ represents an alkyl group of 1 to 8 carbon atoms or an alkoxy group.) And at least one metal chelate having a metal in the center. It is a manufacturing method of the laminated body of Claim 1 or 2 .
The invention according to claim 4 is characterized in that the anchor coat agent for application is added in a proportion of 20 to 500 parts by weight of (2) alkoxysilane with respect to 100 parts by weight of (1) alkoxysilane. And the alkoxysilane of (2) is added in a proportion of 0.2 to 3.0% by weight, and the metal chelate is 0.5 to 30.0% by weight with respect to the alkoxysilane of (1) and (2) The method for producing a laminate according to any one of claims 1 to 3, wherein the laminate is added at a ratio of
The invention described in claim 5 is characterized in that the moisture contained in the anchor coat agent for coating is 0.5 to 1.5 times the theoretical moisture amount necessary for hydrolyzing all alkoxysilanes. It is a manufacturing method of the layered product according to any one of claims 1 to 4 .

  The anchor coating agent for coating of the present invention can easily and efficiently form a highly transparent thin film by coating. In addition, the anchor coating agent for coating of the present invention is characterized by excellent adhesion. For this reason, a film having good adhesion can be obtained when applied to silicone coating. The anchor coating agent for coating of the present invention can be cured at a low curing temperature (100 to 200 ° C.) and has adhesion and transparency. When the anchor coating agent for coating of the present invention is produced, it is not necessary to add an acid catalyst, so that the production method is simple and convenient by the ordinary sol-gel method. Furthermore, the anchor coating agent of the present invention for coating can adjust the water content by the ratio of the hydrophilic solvent and the hydrophobic organic solvent, so that the reaction is relatively stable, and an environment advantageous for adhesion is obtained. Provided.

As the alkoxysilane represented by (1 ) of the present invention, those having a bifunctional group, a trifunctional group or a tetrafunctional group can be used. In order to improve adhesion, trifunctional or tetrafunctional alkoxysilanes are preferred. Alternatively, alkoxysilane having an epoxy group can be used. However, the alkoxysilane represented by said (1) does not have a (meth) acryloyl group.

  Examples of the tetrafunctional alkoxysilane include, but are not limited to, tetramethoxylane and tetraethoxylane.

  Examples of trifunctional alkoxysilanes include trimethoxylane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and isobutyltrimethoxy. Silane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, etc. Absent.

  Bifunctional alkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dimethyldi (n-propoxy) silane, dimethyldi (iso-propoxy) silane, and dimethyldi (n-propoxy) silane. , Dimethyldi (sec-butoxy) silane, dimethyldi (tert-butoxy) silane, dimethyldi (sec-butoxy) silane, diethyldi (n-propoxy) silane, diethyldi (iso-propoxy) silane, diethyldi (n-propoxy) silane, diethyldi Examples include (sec-butoxy) silane, diethyldi (tert-butoxy) silane, diethyldi (sec-butoxy) silane, and the like, but not limited thereto.

  Examples of the alkoxysilane having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxy. Examples thereof include, but are not limited to, propyltriethoxysilane.

As the alkoxysilane represented by (2 ) of the present invention, those having a bifunctional group or a trifunctional group can be used. In order to improve adhesion, a trifunctional alkoxysilane is preferred.

The alkoxysilane of the (2), 3-methacryloxypropyl trimethoxy silane, 3-Metakuriroki shea triethoxysilane, 3-acryloxy propyl trimethoxy silane, 3-acryloxy propyl triethoxy silane, 3-acryloxy Examples thereof include, but are not limited to, propyltrimethoxysilane.

  The organic solvent preferably includes both a hydrophilic solvent and a hydrophobic organic solvent. As the hydrophilic solvent, alcohols such as methanol, ethanol and isopropyl alcohol or ketones such as methyl ethyl ketone can be used. A solvent such as toluene or hexane can be used as the hydrophobic organic solvent. In addition, it is not limited to the above solvents.

As the metal chelate, R ⁴ OH (R ⁴ represents an alkyl group having 1 to 8 carbon atoms) and / or R ⁵ COCH ₂ COR ⁶ (R ⁵ represents an alkyl group having 1 to 8 carbon atoms, and R ⁶ represents carbon. 1 to 8 alkyl groups or alkoxy groups.) And at least one kind of metal chelate having a metal at the center. At this time, examples of the central metal include Al, Ti, Zr, and Sn. For example, diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetate) Nato) Aluminum, monoacetylacetonate bis (ethyl acetoacetate) Aluminum chelate compounds such as aluminum, diisopropoxy bis (ethyl acetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diisopropoxy Examples include, but are not limited to, titanium chelate compounds such as bis (acetylacetone) titanium.

In the anchor coating agent for coating of the present invention, (1) 100 parts by weight of alkoxysilane is added with (2) alkoxysilane in a proportion of 20 to 500 parts by weight, and the alkoxysilanes of (1) and (2) above are added. 0.2 to 3.0 wt% is added, and the metal chelate is added in a proportion of 0.5 to 30.0 wt% with respect to the alkoxysilanes (1) and (2). preferable.
When the alkoxysilane concentration is low, the reaction is insufficient and the film formability may deteriorate. On the other hand, when the alkoxysilane concentration is high, the reaction is fast, the stability of the anchor coating agent is weak, and the adhesion is also poor. Further, when (2) alkoxysilane is outside the range of 20 to 500 parts by weight with respect to 100 parts by weight of (1) alkoxysilane, the anchor coat effect is not sufficiently exhibited, and the adhesion may be weakened. is there. Furthermore, if the amount of the metal chelate added is outside the above range, the reaction may not be accelerated sufficiently (less than 0.5% by weight) or the film formation may be inhibited (over 30.0% by weight).
Furthermore, since the alkoxysilane concentration is 0.2 to 3.0% by weight, the alkoxysilane hydrolysis reaction rate can be adjusted.

  In the anchor coating agent solution for coating of the present invention, the moisture contained therein is preferably 0.5 to 1.5 times the theoretical moisture amount necessary for hydrolyzing all alkoxysilanes. When the amount of water increases, the reaction is accelerated, the adhesion between the anchor coating agent and silicone is deteriorated, and the pot life of the anchor coating agent is shortened. When the amount of water decreases, the reaction becomes insufficient, and the adhesion between the anchor coating agent and silicone also deteriorates. That is, by achieving the above water content, the adhesion between the anchor coating agent and silicone is further improved.

A mode in which the curing temperature of the anchor coat layer formed by the anchor coating agent solution for coating is 100 to 200 ° C. and the curing time is 10 to 60 seconds is preferable.
Since plastic substrates (especially optical films) are susceptible to heat shrinkage, heat wrinkles increase when the curing time is long or the curing temperature is high. Since the present invention has the above-described features, it can improve heat wrinkles.

Moreover, this invention provides the laminated body which provided the anchor-coat layer on the base material using the anchor-coat agent solution for application | coating of this invention mentioned above, and also formed the silicone layer on this anchor-coat layer.
The anchor coat agent for coating of the present invention can form an anchor coat layer by, for example, stirring on a room temperature for 1 hour, coating on a base material, heat drying and curing at 100 to 200 ° C. On top of that, a silicone layer is made. The obtained laminate has excellent adhesion.

  As the base material of the present invention, cellulose triacetate (TAC) film, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (PA), polycarbonate (PC), polyacryl (PMMA), nylon (Ny) And plastic film base materials such as polyethersulfone (PES), polyvinyl chloride (PVC), and polypropylene (PP), and glass base materials.

  The organic polymer constituting the plastic film base material can be used in the form of a known additive, for example, an ultraviolet absorber, a plasticizer, a colorant, an antioxidant, a flame retardant, a lubricant and the like. . The film substrate may be a single layer or a laminate of a plurality of organic polymers. Moreover, although the thickness is not specifically limited, 25-300 micrometers is preferable.

A hard coat layer may be provided between the base material and the anchor coat layer.
The hard coat layer is not particularly limited as long as it has high transparency and improves the surface hardness and mechanical strength of the antireflection material, and a known one can be used.

As the silicone-based material for forming the silicone layer, a curing reaction type silicone coating agent such as an addition curing type or a UV curing type can be used. Specifically, Toray Dow co-Ningu Co., Ltd. SRX211, LTC750A, LTC760A, BY24-510, Shin-Etsu Chemical Co., Ltd. KS774, KS847, KS5508, Momentive Performance Materials made TPR6700, TPR6702, TPR6710, TPR6721, TPR6500, UV-POLY200, UV-POLY201, etc. manufactured by Arakawa Chemical Industries, Ltd. can be used, but these are not limited.

Moreover, in the silicone layer forming material, various curing catalysts and photoinitiators are used according to the curing type, and are appropriately added. For example, Toray Dow co-Ningu Co., Ltd. SRX212, NC-25, such as BY24-835, such as PL-50T manufactured by Shin-Etsu Chemical Co., Ltd., such as Momentive Performance Materials Inc. CM670, UV9380, Arakawa Chemical Industry Co., Ltd. UV-CATA211 etc. made from UV can be used as a curing catalyst and photoinitiator.

  Further, a surface conditioner, a leveling agent, an adhesion improver, a photosensitizer and the like can be added as additives to the silicone layer forming material.

  In addition, the coating process applied to the present invention includes a wet film forming method, and if necessary, a drying process for removing the solvent is provided after the coating process, and an ionizing radiation irradiation process and a heating process are performed as a curing process. Is provided. As a coating method, a coating method using a roll coater, a reverse roll coater, a gravure coater, a micro gravure coater, a knife coater, a bar coater, a wire bar coater, a die coater, or a dip coater can be used.

Using a 75 μm thick biaxially stretched polyethylene terephthalate film (Merinex S manufactured by Teijin) as a film substrate, an anchor coating agent having the following composition was applied by a bar coater, and after application, 150 ° C. and 30 seconds drying and curing in an oven, An anchor coat layer was formed. The film thickness of the obtained anchor coat layer was 50 nm.
<Anchor coating agent (coating solution)>
3 Metakuriroki Shi aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical) 2.5 parts by weight of tetraethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.5 parts by weight of aluminum chelate BY24-846E
(Dow co Ningu Ltd. 40 wt%) 2.5 parts by weight of toluene and methyl ethyl ketone (1: 1 wt%) 492 parts by weight of distilled water (together with moisture contained in the solvent) mixing 1.2 parts by weight each component Then, after stirring for about 1 hour, an anchor coating agent coating solution was obtained.

Next, a silicone functional layer-forming material having the following composition is applied to the film substrate on which the anchor coat layer has been formed with a bar coater, and after application, it is dried and cured at 100 ° C. for 1 minute in an oven. A functional layer was formed by irradiating ultraviolet rays with an integrated exposure amount of 500 mJ / cm ² using a UV curing apparatus. The film thickness of the obtained silicone functional layer was 98 nm.
<Silicone functional layer forming material (coating solution)>
Silico Lease UV POLY200 (Arakawa Chemical Industries, Ltd.) 4 parts by weight Silico Lease UV CVATA211
(Photoinitiator / made by Momentive) 0.2 weight part Ethyl acetate 48 weight part n-hexane 48 weight part By the above, the silicone functional film of Example 1 was produced.

[Evaluation of adhesion to substrate]
After rubbing the surface of the silicone functional layer immediately after curing and the cured silicone functional layer after storage for half a year at room temperature with the index finger 10 times (reciprocating), apply black magic ink to change the surface condition. Observed and evaluated according to the following criteria.
◎: Play the magic ink on the entire surface of the cured silicone functional layer.
○: A little magic ink is applied to the rubbed part.
◇: Magic ink is applied to the rubbed area.
△: Magic ink is applied ~ Silicone functional layer partially falls off,
X: The silicone functional layer falls off.

[Measurement of spectral transmittance]
The obtained silicone functional film uses an automatic spectrophotometer (manufactured by Hitachi, Ltd., U-4000), and under the conditions of a C light source and a 2-degree visual field, the spectral transmittance at an incident angle of 5 ° with respect to the low refractive index layer forming surface. Was measured.

[Promotion evaluation of adhesion to substrate]
The cured silicone functional layer was stored in an environment of 40 ° C. and 90% humidity for 1 month, and then allowed to stand at 25 ° C. and 50% humidity for 1 day. After rubbing the surface of the silicone functional layer 10 times (reciprocating) with the index finger, black magic ink was applied, and the surface state was observed and evaluated according to the above criteria.

[Promotion evaluation of adhesion to substrate 1]
The silicone functional layer after curing was immersed in distilled water at 90 ° C. for 5 hours and then left for 1 day at 25 ° C. and 50% humidity. After rubbing the surface of the silicone functional layer 10 times (reciprocating) with the index finger, black magic ink was applied, and the surface state was observed and evaluated according to the above criteria.

[Measurement of antifouling properties]
Oily black magic ink is applied on the surface of the obtained silicone functional layer and the cured silicone functional layer after storage for 6 months, and lightly rubbed 10 times with Kim Towel (manufactured by Nippon Paper Crecia). The surface condition was observed and evaluated according to the following criteria.
A: Magic ink is completely gone.
B: Magic ink remains slightly,
C: Magic ink remains.
The evaluation results of Example 1 are shown in Table 1. From the results, it was found that when the anchor coat layer was present, the obtained silicone functional film had antifouling property, high transparency and excellent adhesion.

Comparative Example 1

  In Example 1, an anchor coat layer was not formed, and other than that was operated in the same manner as in Example 1 to obtain a silicone functional film. The evaluation results of Comparative Example 1 are shown in Table 1. When there was no anchor coat layer, it was confirmed that the obtained silicone functional film had no adhesion and was peeled off.

The same operation as that for coating the anchor coat layer in Example 1 was performed to obtain an anchor coat layer. The silicone functional material (coating liquid) shown below was used to apply the silicone functional material with a bar coater. After coating, the silicone functional material was dried and cured in an oven at 150 ° C. for 30 seconds to form a silicone functional layer. . The film thickness of the obtained silicone functional layer was 92 nm.
<Silicone functional layer forming material (coating solution)>
Evaluation of the silicone LTC750A (Toray Dow co manufactured Ningu Co.) 2 parts by weight of the silicone catalyst SRX-212 (manufactured by Toray Dow co manufactured Ningu Corporation) 0.02 parts by weight Toluene 49 parts by weight Methyl ethyl ketone 49 parts by weight Example 2 The results are shown in Table 1. From the results, it was found that when the anchor coat layer was present, the obtained silicone functional film had excellent adhesion, antifouling property and high transparency.

Comparative Example 2

  In Example 2, an anchor coat layer was not formed, and other than that was operated in the same manner as in Example 2 to obtain a silicone functional film. The evaluation results of Comparative Example 2 are shown in Table 1. When there was no anchor coat layer, it was confirmed that the obtained silicone functional film did not have adhesiveness and peeled.

Using a biaxially stretched polyethylene terephthalate film (Melinex S, manufactured by Teijin) with a thickness of 75 μm as the film base, apply the anchor coating agent of the following composition with a bar coater, and then dry and cure in an oven at 150 ° C. for 30 seconds. An anchor coat layer was formed. The film thickness of the obtained anchor coat layer was 50 nm.
<Anchor coating agent (coating solution)>
3-acryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight tetraethoxylane (manufactured by Tokyo Chemical Industry) 2.5 parts by weight aluminum chelate BY24-846E
(Dow co Ningu Ltd. 40 wt%) 2.5 parts by weight of toluene and methyl ethyl ketone (1: 1 wt%) 492 parts by weight of distilled water (together with moisture contained in the solvent) mixing 1.2 parts by weight each component Then, after stirring for about 1 hour, an anchor coating agent coating solution was obtained.

Next, a silicone functional layer-forming material having the following composition is applied to the film substrate on which the anchor coat layer has been formed with a bar coater. After application, the film is dried and cured in an oven at 150 ° C. for 30 seconds to provide silicone functionality. A layer was formed. The film thickness of the obtained silicone functional layer was 95 nm.
<Silicone functional layer forming material (coating solution)>
The silicone LTC750A (manufactured by Toray Dow co Ningu Ltd.) 2 parts by weight of the silicone catalyst SRX-212 (manufactured by Toray Dow co Ningu Ltd.) 0.02 parts by weight Toluene 49 parts by weight Methyl ethyl ketone 49 parts by weight or more, Example No. 3 silicone functional film was prepared. From the evaluation result of Example 3, when there is an anchor coat layer, the obtained silicone functional film has excellent adhesion, high transparency and antifouling properties.

In Example 3, a silicone functional film was obtained in the same manner as in Example 1 except that the following anchor coating agent (coating solution) was used. From the evaluation results (Table 1), the silicone functional film obtained when the anchor coat layer is present has adhesion, antifouling properties and transparency.
<Anchor coating agent (coating solution)>
3 Metakuriroki Shi aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight of 3-glycidoxypropyl triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight of aluminum chelate BY24-846E
(Dow co Ningu Ltd. 40 wt%) 2.5 parts by weight of toluene and methyl ethyl ketone (1: 1 wt%) 492 parts by weight of distilled water (together with moisture contained in the solvent) 1.2 parts by weight

A silicone functional film was obtained in the same manner as in Example 4 except that the following anchor coating agent (coating solution) was used in Example 4 and the same. From the evaluation results (Table 1), it was found that when the amount of the alkoxysilane amount specified in claim 4 was exceeded, the adhesion of the obtained silicone functional film was weakened.
<Anchor coating agent (coating solution)>
3 Metakuriroki Shi aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 4.5 parts by weight of 3-glycidoxypropyl triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by weight aluminum chelate BY24-846E
(Dow co Ningu Ltd. 40 wt%) 2.5 parts by weight of toluene and methyl ethyl ketone (1: 1 wt%) 492 parts by weight of distilled water (together with moisture contained in the solvent) 1.2 parts by weight

A silicone functional film was obtained in the same manner as in Example 4 except that the following anchor coating agent (coating solution) was used in Example 4 and the same. From the evaluation results (Table 1), it was confirmed that the adhesiveness of the obtained silicone functional film was weak when it was less than the range of the alkoxysilane amount specified in claim 4.
<Anchor coat (coating solution)>
3 Metakuriroki Shi aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by weight of 3-glycidoxypropyl triethoxy silane 4.5 parts by weight aluminum chelate BY24-846E
(Dow co Ningu Ltd. 40 wt%) 2.5 parts by weight of toluene and methyl ethyl ketone (1: 1 wt%) 492 parts by weight of distilled water (together with moisture contained in the solvent) 1.2 parts by weight

A silicone functional film was obtained in the same manner as in Example 4 except that the following anchor coating agent (coating solution) was used in Example 4 and the same. From the evaluation results (Table 1), when the amount of the metal chelate amount specified in claim 4 is exceeded, the adhesion of the obtained silicone functional layer film is weak.
<Anchor coating agent (coating solution)>
3 Metakuriroki Shi aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight of 3-glycidoxypropyl triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight of aluminum chelate BY24-846E
(Dow co Ningu Ltd. 40 wt%) 5.0 parts by weight of toluene and methyl ethyl ketone (1: 1 wt%) 488 parts by weight of distilled water (together with moisture contained in the solvent) 1.2 parts by weight

A silicone functional film was obtained in the same manner as in Example 4 except that the following anchor coating agent (coating solution) was used in Example 4 and the same. From the evaluation results (Table 1), the adhesiveness of the silicone functional film obtained when the amount is less than the range of the metal chelate amount specified in claim 4 is also weak.
<Anchor coating agent (coating solution)>
3 Metakuriroki Shi aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight of 3-glycidoxypropyl triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight of aluminum chelate BY24-846E
(Dow co Ningu Ltd. 40 wt%) 0.05 parts by weight of toluene and methyl ethyl ketone (1: 1 wt%) 495 parts by weight of distilled water (together with moisture contained in the solvent) 1.2 parts by weight

A silicone functional film was obtained in the same manner as in Example 4 except that the following anchor coating agent (coating solution) was used in Example 4 and the same. From the evaluation results (Table 1), when the amount of water specified in claim 5 is exceeded, the resulting silicone functional film reacts excessively, resulting in poor adhesion.
<Anchor coating agent (coating solution)>
3 Metakuriroki Shi aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight of 3-glycidoxypropyl triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight of aluminum chelate BY24-846E
(Dow co Ningu Ltd. 40 wt%) 2.5 parts by weight of toluene and methyl ethyl ketone (1: 1 wt%) 491 parts by weight of distilled water (together with moisture contained in the solvent) 2.0 parts by weight

A silicone functional film was obtained in the same manner as in Example 4 except that the following anchor coating agent (coating solution) was used in Example 4 and the same. From the evaluation results (Table 1), it was confirmed that the silicone functional film obtained as being less than the amount of water specified in claim 5 was insufficiently reacted, resulting in poor adhesion.
<Anchor coating agent (coating solution)>
3 Metakuriroki Shi aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight of 3-glycidoxypropyl triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight of aluminum chelate BY24-846E
(Dow co Ningu Ltd. 40 wt%) 2.5 parts by weight of toluene and methyl ethyl ketone (1: 1 wt%) 492 parts by weight of distilled water (together with moisture contained in the solvent) of 0.5 parts by weight anchor coating agent In particular, when the water content is other than 0.5 to 1.5 times the theoretical water content necessary for hydrolysis, the adhesiveness of the obtained silicone functional film becomes weak.

  From the above examples, it was found that the silicone functional film coated thereon using the coating anchor coating agent of the present invention has excellent adhesion, high transparency and antifouling properties.

Claims (5)

In an organic solvent, (1) tetramethoxylane, tetraethoxylane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy An alkoxysilane selected from silane and 3-glycidoxypropyltriethoxysilane; and (2) 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3 Applying an anchor coating agent for coating containing an alkoxysilane selected from acryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane and a metal chelate onto a plastic film-based substrate;
Curing the coating anchor coat agent at a curing temperature of 100 to 200 ° C. and a curing time of 10 to 60 seconds to form an anchor coat layer;
Applying a silicone coating agent on the anchor coating layer to form a silicone layer;
The manufacturing method of the laminated body characterized by comprising. The method for producing a laminate according to claim 1, wherein the organic solvent contains both a hydrophilic solvent and a hydrophobic organic solvent. The metal chelate has the general formula R ⁴ OH (R ⁴ represents an alkyl group having 1 to 8 carbon atoms) and / or R ⁵ COCH ₂ COR ⁶ (R ⁵ represents an alkyl group having 1 to 8 carbon atoms, and R ⁶ represents carbon. The laminate according to claim 1 or 2, wherein the compound is a compound represented by 1 to 8), and is a metal chelate having a metal at the center. Manufacturing method . The anchor coat agent for application is added in a proportion of 20 to 500 parts by weight of (2) alkoxysilane with respect to 100 parts by weight of (1) alkoxysilane, and 0 (1) and (2) alkoxysilane is 0. The metal chelate is added at a rate of 0.5 to 30.0% by weight with respect to the alkoxysilanes (1) and (2). The manufacturing method of the laminated body of any one of Claim 1 thru | or 3 . 5. The water content contained in the coating anchor coating agent is 0.5 to 1.5 times the theoretical water content necessary for hydrolyzing all alkoxysilanes . 5. The manufacturing method of the laminated body as described in a term .