TWI473855B - Resin composition, fluorine-based resin composite including the same and method for manufacturing the same - Google Patents

Description

Resin composition, fluorine-based resin composite material containing the same, and method for producing the same

The present invention relates to a resin composition of a fluorine-based resin, a fluorine-based resin composite containing the resin composition, and a method for producing the same.

In order to make the outdoor fabric have good weather resistance, a fluorine-based resin having good weather resistance is often applied to a substrate. However, the fluorine-based resin layer only physically closes the substrate, so that the adhesion between the fluorine-based resin layer and the substrate is not good. After a period of time, the fluorine-based resin layer will gradually peel off, and the substrate loses its original weather resistance.

On the other hand, the fluorine-based resin layer may be bonded to the substrate by an adhesive. However, since the fluorine-based resin has a small number of hydrogen atoms in the main chain, it is difficult to achieve sufficient adhesion strength by bonding the fluorine-based resin layer to the substrate by a general adhesive. If the weather resistance of the adhesive itself is insufficient, the fluorine-based resin layer may peel off even when used for a long period of time.

Therefore, there is a need in the related art for an adhesive having high adhesion to a fluorine-based resin and having good weather resistance, in order to improve the service life of the fluorine-based resin composite.

The present invention provides a resin composition which has high adhesion to a fluorine-based resin and has good weather resistance, and can effectively adhere a fluorine-based resin to various substrates.

One aspect of the present invention provides a resin composition for a fluorine-based resin comprising an epoxy resin and an amine polyoxyalkylene. The amine polyoxyalkylene is formed by a hydrolysis condensation reaction of an amino alkoxydecane with an aromatic alkoxydecane. The molar ratio of the epoxy group of the resin composition to the epoxy resin is from 0.06 to 0.77.

According to an embodiment of the present invention, the molar ratio of the amino alkoxydecane to the aromatic alkoxydecane is 1/3 to 1/1.

According to an embodiment of the invention, the weight ratio of the amine polysiloxane to the epoxy resin is from 1:20 to 4.5:10.

According to an embodiment of the present invention, the content of the inorganic cerium of the resin composition is from 1.0 to 5.0% by weight.

According to an embodiment of the present invention, the amino alkoxydecane has the formula H ₂ NR ³ -Si(R ² ) _a (OR ¹ ) _3-a , wherein R ¹ and R ² are H or a C1-C4 alkyl group. , a is 0 or 1, R ³ is a C1-C10 alkyl group or R ⁵ -NH-R ⁴ , and R ⁴ and R ⁵ are a C1-C10 alkyl group.

According to an embodiment of the present invention, the aromatic alkoxydecane has the formula R ⁸ -Si(R ⁷ ) _b (OR ⁶ ) _3-b , wherein R ⁶ and R ⁷ are H or a C1-C4 alkyl group, b R 0 or 1, R ⁸ is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and combinations thereof.

Another aspect of the present invention provides a method for producing a resin composition for a fluorine-based resin, comprising the following steps. The amine alkoxy decane is mixed with an aromatic alkoxy decane to form an amine polyoxy siloxane. The epoxy resin and the amine polysiloxane are mixed to form a resin composition in which the molar ratio of the epoxy group of the resin composition to the epoxy resin is from 0.06 to 0.77.

According to one embodiment of the invention, the amino alkoxy decane and the aromatic The alkoxydecane has a molar ratio of 1/3 to 1/1.

According to an embodiment of the invention, the weight ratio of the amine polysiloxane to the epoxy resin is from 1:20 to 4.5:10.

According to an embodiment of the present invention, the amino alkoxydecane has the formula H ₂ NR ³ -Si(R ² ) _a (OR ¹ ) _3-a , wherein R ¹ and R ² are H or a C1-C4 alkyl group. , a is 0 or 1, R ³ is a C1-C10 alkyl group or R ⁵ -NH-R ⁴ , and R ⁴ and R ⁵ are a C1-C10 alkyl group.

According to an embodiment of the present invention, the aromatic alkoxydecane has the formula R ⁸ -Si(R ⁷ ) _b (OR ⁶ ) _3-b , wherein R ⁶ and R ⁷ are H or a C1-C4 alkyl group, b R 0 or 1, R ⁸ is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and combinations thereof.

According to an embodiment of the invention, the amino alkoxydecane and the aromatic alkoxy decane are mixed in an acidic environment.

According to one embodiment of the invention, the pH of the acidic environment is from 1 to 3.

Another aspect of the present invention provides a method for producing a fluorine-based resin composite comprising the following steps. A substrate is provided. An adhesive layer is formed on the substrate, wherein the adhesive layer comprises the above resin composition. A fluorine-based resin layer having a hydroxyl group is then applied to the adhesive layer in an environment of 90 to 120 °C.

Another aspect of the present invention provides a fluorine-based resin composite obtained by the above production method.

According to an embodiment of the invention, the substrate comprises polyester, glass fibers or a combination thereof.

In the following, a plurality of embodiments of the present invention will be disclosed in the drawings. For the sake of explanation, many practical details will be explained in the following description. However, it should be understood that these practical details are not intended to limit the invention. That is, in some embodiments of the invention, these practical details are not necessary. In addition, some of the conventional structures and elements are shown in the drawings in a simplified schematic manner in order to simplify the drawings.

One aspect of the present invention provides a method for producing a resin composition for a fluorine-based resin, which comprises the following steps. The amine alkoxy decane is mixed with an aromatic alkoxy decane to form an amine polyoxy siloxane. The epoxy resin and the amine polysiloxane are mixed to form a resin composition in which the molar ratio of the epoxy group of the resin composition to the epoxy resin is from 0.06 to 0.77. In other words, the synthesized resin composition still contains an unreacted epoxy group. The unreacted epoxy group reacts with the hydroxyl group of the fluorine-based resin to form a chemical bond, thereby enhancing the adhesion between the resin composition and the fluorine-based resin. Also, the amine polyoxyalkylene can provide good heat resistance. As described above, the resin composition of the present invention has high adhesion to a fluorine-based resin and also has good heat resistance, and can effectively help the fluorine-based resin adhere to various substrates. Specific embodiments of the respective steps of the above manufacturing method are detailed below.

First, at least one amino alkoxydecane and at least one aromatic alkoxy decane are mixed and subjected to a hydrolysis condensation reaction to form an amine polysiloxane. In detail, the alkoxy group of the amino alkoxydecane and the aromatic alkoxydecane may be hydrolyzed to form a hydroxyl group, and then dehydrated and condensed to form a oxime bond. In a macroscopic view, after the hydrolysis and condensation reaction of the amino alkoxy decane with the aromatic alkoxy decane, an inorganic oxime structure and an organic functional group (ie, an aromatic group, an amine group, etc.) are formed. Amine polyoxyalkylene.

The amino alkoxydecane has the formula H ₂ NR ³ -Si(R ² ) _a (OR ¹ ) _3-a , wherein R ¹ and R ² are H or a C1-C4 alkyl group, and a is 0 or 1, R ³ is a C1-C10 alkyl group or R ⁵ -NH-R ⁴ , and R ⁴ and R ⁵ are a C1-C10 alkyl group. The amino alkoxydecane may comprise a primary amine group, a secondary amine group or a combination thereof. For example, the amino alkoxydecane can be N-[3-(trimethoxysilyl)propyl]ethylenediamine or 3-aminopropyltri 3-aminopropyltriethoxysilane. The amine group of the amino alkoxydecane may undergo a ring opening reaction with an epoxy group of the epoxy resin to form a chemical bond.

The aromatic alkoxydecane has the formula R ⁸ -Si(R ⁷ ) _b (OR ⁶ ) _3-b , wherein R ⁶ and R ⁷ are H or a C1-C4 alkyl group, b is 0 or 1, and the R ⁸ system is A group of freely substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and combinations thereof. That is, R ^{8 of the} aromatic alkoxydecane has at least one phenyl group, and the aromatic alkoxydecane has good heat resistance. The aromatic alkoxy decane is, for example, phenyltriethoxysilane or naphthyltriethoxysilane.

In one embodiment, the molar ratio of the amino alkoxydecane to the aromatic alkoxydecane is from 1/3 to 1/1. If the ratio of aromatic alkoxy decane to the whole is too high (ie, the molar ratio is less than 1/3), the molecular chain of the amine polyoxyalkylene will be too long, resulting in the collision probability of subsequent amine groups and epoxy groups. Lower, the reaction time increases. Therefore, the molar ratio of the amino alkoxydecane to the aromatic alkoxydecane is preferably more than 1/3.

In one embodiment, the amino alkoxydecane and the aromatic alkoxy decane are mixed in an acidic environment. The pH of the acidic environment is, for example, from 1 to 3. The reaction temperature is, for example, 30 to 50 °C. Under the above process conditions, The amine-based polyoxyalkylene formed contains an inorganic oxime structure and can provide good heat resistance.

After the formation of the amine siloxane, the epoxy resin and the amine polyoxyalkylene are further mixed to form a resin composition. In detail, the exposed amine group of the amine polyoxyalkylene structure can undergo a ring-opening reaction with an epoxy group of the epoxy resin to form a resin composition containing an organic crosslinked structure, an inorganic oxime structure, and an epoxy group. The epoxy group can be reacted with a hydroxyl group of the fluorine-based resin to form a chemical bond, and the adhesion between the resin composition and the fluorine-based resin can be enhanced.

The epoxy resin is, for example, a bisphenol A type epoxy resin, a bisphenol P type epoxy resin, a brominated bisphenol type epoxy resin, a biphenyl type epoxy resin, a lipid cyclic epoxy resin, or a glycidyl ester type. Epoxy resin, glycidylamine type epoxy resin, other suitable epoxy resin or a combination thereof, but are not limited thereto.

It is important that the molar ratio of the epoxy resin obtained to the epoxy resin of the epoxy resin is from 0.06 to 0.77. That is, after the amino alkoxydecane is reacted with the epoxy resin, the amount of epoxy groups (relative to the number of epoxy groups of the original epoxy resin) is left from 6% to 77%. For example, the epoxy equivalent of the epoxy resin and the resin composition can be separately tested by an epoxy equivalent method. "Epoxy equivalent" means the number of grams of epoxy resin containing one equivalent of an epoxy group. The ratio of the epoxy equivalent of the epoxy resin to the resin composition is the molar ratio of the epoxy resin composition to the epoxy group.

The epoxy equivalent measurement method is briefly described below. First, hydrochloric acid is added to the test object, all epoxy groups are opened, and unreacted hydrochloric acid molecules are titrated by a sodium hydroxide methanol solution to calculate an epoxy equivalent. The calculation method is as shown in the following formula (1):

W is the weight of the analyte (unit: gram), and N is the concentration of the standard sodium hydroxide methanol solution (unit: equivalent / liter). Vb is the consumption of sodium hydroxide (ml) in the blank test, and Vs is the consumption of sodium hydroxide (ml) when the analyte is titrated. If the amount of epoxy groups of the analyte is larger, the amount of sodium hydroxide consumed when the analyte is titrated is less (that is, less unreacted hydrochloric acid molecules). If the amount of epoxy groups of the analyte is smaller, the amount of sodium hydroxide consumed when the analyte is titrated is increased (that is, the amount of unreacted hydrochloric acid molecules is larger). Therefore, the epoxy equivalent of the analyte having a large amount of epoxy groups is low, and the epoxy equivalent of the analyte having a small amount of epoxy groups is high.

The specific epoxy equivalent measurement method is exemplified as follows. First, 8.5 ml of hydrochloric acid and 50 ml of pyridine were combined to form a hydrochloric acid-pyridine solution. 25 ml of a 0.2 N hydrochloric acid-pyridine solution was added to an Erlenmeyer flask containing 0.5 g of the resin composition, and the temperature was kept at 40 ° C for 40 minutes. Then, the Erlenmeyer flask was refluxed in an oil bath at 115 ° C for 30 minutes, cooled to room temperature, and 25 ml of methanol was added to the Erlenmeyer flask. Subsequently, a phenolphthalein indicator is added and titrated with sodium hydroxide to obtain a consumption amount (Vs) of sodium hydroxide when the analyte is titrated. Further, 25 ml of a 0.2 N hydrochloric acid-pyridine solution was mixed with 25 ml of methanol, and titrated in the same manner as above to obtain a sodium hydroxide consumption (Vb) in the blank test. Then, by the formula (1), the epoxy equivalent of the analyte can be calculated.

In one embodiment, the weight ratio of amine polysiloxane to epoxy resin is from 1:20 to 4.5:10. If the weight ratio of the amine polyoxyalkylene to the epoxy resin is greater than 4.5:10 (ie, the weight percentage of the amine polyoxyalkylene to the total weight is greater than 31%), the amount of remaining epoxy groups is too small and will be severe. Affecting resin composition Adhesion to fluorine resin. However, if the weight ratio of the amine polysiloxane to the epoxy resin is less than 1:20 (that is, the weight percentage of the amine polysiloxane is less than 0.48%), the crosslinking ratio of the epoxy resin is low and inorganic. Too little oxygen structure will affect the rigidity and heat resistance of the resin composition. Therefore, the weight of the amine polyoxyalkylene and the epoxy resin is preferably from 1:20 to 4.5:10.

Another aspect of the present invention provides a resin composition for a fluorine-based resin comprising an epoxy resin and an amine polyoxyalkylene. In one embodiment, there is no solvent in the resin composition. For specific embodiments of the epoxy resin and the amine polyoxyalkylene, please refer to the above embodiments. Since the resin composition contains an epoxy group which can react with the hydroxyl group of the fluorine-based resin, a good adhesion can be formed between the resin composition and the fluorine-based resin.

In one embodiment, the resin composition has an inorganic cerium content of 1.0 to 5.0 wt%. For example, the resin composition after hardening can be subjected to EDX elemental analysis to obtain an inorganic cerium content. Alternatively, the cured resin composition may be heated to 700 ° C at a temperature increase rate of 10 ° C / min using a thermogravimetric analysis in an air atmosphere. The residual weight of the analyte at 700 ° C is the inorganic cerium content.

Referring to Fig. 1, another aspect of the present invention provides a method for producing a fluorine-based resin composite material 10, which comprises the following steps.

First, a substrate 110 is provided. In an embodiment, the substrate 110 comprises polyester, fiberglass, or a combination thereof. Specifically, the substrate 110 is, for example, a polyester cloth or a glass cloth, but is not limited thereto.

Then, an adhesive layer 120 is formed on the substrate 110, wherein the adhesive layer 120 contains the above-described resin composition. The adhesive layer 120 can be formed on the substrate 110, for example, using any coating method. In an embodiment, the connection The thickness of the primer layer 120 is 0.05 to 0.15 mm. Of course, a heating step may be performed after the formation of the adhesive layer 120, so that the adhesive layer 120 is in a semi-wet and semi-dry unfilmed state (that is, in an incompletely dried state). In one embodiment, the heating temperature is from 85 to 100 °C.

After the formation of the adhesive layer 120, the fluorine-based resin layer 130 having a hydroxyl group is then deposited on the adhesive layer 120 in an environment of 90 to 120 °C. Specifically, a fluorine-based resin layer 130 having a hydroxyl group may be first formed on the adhesive layer 120, and then a drying process at a heating temperature of 90 to 120 ° C may be performed. In one embodiment, the fluorine-based resin layer 130 having a hydroxyl group has a thickness of 0.20 to 0.40 mm.

The material of the fluorine-based resin layer 130 having a hydroxyl group is a fluorine-based resin coating material, and may contain a fluorine-based resin having a hydroxyl group and a solvent.

The fluorine-based resin having a hydroxyl group is, for example, a copolymer obtained by polymerizing a hydroxyl group-containing polyethylene and a fluorocarbon polymer. The fluorocarbon polymer is, for example, polyvinyl fluoride (PVF), polyvinylidene difluoride (PVDF), polytetrafluoroethylene (PTFE), or ethylene tetrafluoroethylene (ETFE). , but not limited to this. The solvent is, for example, butyl acetate, xylene, coal-tar naphtha or a combination thereof.

The fluorine-based resin coating material is, for example, a fluorocarbon resin commercially available as ZEFFLE GK570, GK500, GK510, GK550, or GK580, but is not limited thereto. The partial chemical structure of such a fluorocarbon resin having a hydroxyl group is as shown in the chemical formula (1).

Y in the formula (1) may be any suitable functional group. The m, n, and x values can be any integer, respectively.

In one embodiment, the fluororesin coating has a hydroxyl value of 30 to 100 mgKOH/g resin. In one embodiment, the fluororesin coating has an acid value of 1 to 13 mgKOH/g resin. In one embodiment, the fluororesin coating has a solid content of 45 to 70% by weight. In one embodiment, the fluororesin coating has a viscosity of 100 to 600 mPa-s.

After the fluorine-based resin layer 130 having a hydroxyl group is formed on the adhesive layer 120, the laminated structure of the substrate 110, the adhesive layer 120, and the fluorine-based resin layer 130 can be subjected to a hot pressing step to further improve the subsequent effect. In one embodiment, the maximum temperature of the hot press is from 90 to 120 °C. In one embodiment, the pressurizing pressure is 15 kg or more.

Example

The following examples are intended to be illustrative of specific aspects of the invention, and are intended to be The following examples are not intended to limit the invention.

Comparative Example 1: Fluororesin composite material without an adhesive layer (the base material was a polyester cloth)

First, apply a fluorine resin coating (Model: ZEFFLE GK570, Taiwan Manufactured by Bay Daikin Advanced Chemical Co., Ltd., acid price 64 mgKOH/g resin, hydroxyl value 55 to 65 mgKOH/g resin) on polyester cloth, and dried at 90 ° C for 5 minutes. The thickness of the formed fluorine-based resin layer was 0.3 mm. Next, the polyester cloth and the fluorine-based resin laminated structure were heat-pressed at 90 ° C for 15 seconds under a pressure of 15 kg. Further, the obtained fluorine-based resin composite material was tested for 90° peel strength in accordance with the test specification ISO2411 (clamp spacing: 7.5 cm, test speed: 100 ± 10 mm/min). The 90-degree peel strength of the fluorine-based resin composite material of Comparative Example 1 was 15.52 N.

Comparative Example 2: a fluorine-based resin composite material in which an adhesive layer is an epoxy resin (the base material is a polyester cloth)

First, a bisphenol A type epoxy resin (model: NPEL 128, manufactured by Nanya Corporation) was coated on a polyester cloth, and dried at 90 ° C for 1 minute. The thickness of the epoxy layer formed was 0.1 mm. Then, a fluorine-based resin coating (model: ZEFFLE GK570, manufactured by Taiwan Daikin Advanced Chemical Co., Ltd., acid value 64 mgKOH/g resin, hydroxyl value 55 to 65 mgKOH/g resin) was applied to the epoxy resin layer, and then Dry at 90 ° C for 5 minutes. The thickness of the formed fluorine-based resin layer was 0.3 mm. Next, the polyester cloth, the epoxy resin layer, and the fluorine-based resin laminated structure were heat-pressed at 90 ° C under a pressure of 15 kg for 180 seconds. Further, the obtained fluorine-based resin composite material was tested for 90° peel strength in accordance with the test specification ISO2411 (clamp spacing: 7.5 cm, test speed: 100 ± 10 mm/min). The 90-degree peel strength of the fluorine-based resin composite material of Comparative Example 2 was 16.84 N.

Comparative Example 3: Fluorine-based resin composite material (base material) of KBM-303 For polyester cloth)

In Comparative Example 3, a fluorine-based resin composite material was produced by the method described in Comparative Example 2, except that the adhesive of the model KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd. of Japan was used in Comparative Example 3. The obtained fluorine-based resin composite material was tested for 90° peel strength in accordance with the test specification ISO2411 (clamp spacing: 7.5 cm, test speed: 100 ± 10 mm/min). The 90-degree peel strength of the fluorine-based resin composite material of Comparative Example 3 was 29.64 N.

Experimental Example 1-3: Fluorine-based resin composite in which the adhesive layer was a resin composition (the base material was a polyester cloth)

Experimental Example 1-3 A fluorine-based resin composite material was produced by the method described in Comparative Example 2, except that the adhesive used in Experimental Example 1-3 was the resin composition of the present invention.

The preparation process of the resin composition is as follows. First, N-[3-(trimethoxyindolyl)propyl]ethylenediamine having a molar ratio of 1:1 was mixed with triethoxybenzophenan, and stirred at 40 ° C for 24 hours to obtain an amine group polymerization. Oxane. Then, different ratios (10 wt%, 20 wt%, 30 wt% of the total weight of the amine polysiloxane) to the bisphenol A epoxy resin (Model: NPEL 128, respectively) were added. The resin composition of Experimental Example 1-3 was obtained by stirring at 40 ° C for 12 hours in the same manner as in the epoxy resin of Comparative Example 2. The composition, epoxy equivalent and epoxy molar ratio are listed in Table 1.

^a is the weight percentage of the amine polyoxymethane to the total weight (ie the weight of the epoxy resin and the amine polyoxyalkylene)

^b Calculate the epoxy equivalent according to the above epoxy equivalent determination method

^c is the molar ratio of the epoxy composition of the resin composition to the epoxy resin

In order to understand the reaction state of the epoxy resin and the amine polyoxyalkylene oxide, the resin compositions of Comparative Example 2, Experimental Example 1, and Experimental Example 3 were identified by infrared spectroscopy, and the results were as shown in 2(a)-2(c). The figure shows. In the characteristic peak of the epoxy group (914 cm ^-1 ), the magnitude relationship of the characteristic peak intensity was in the order of Comparative Example 2, Experimental Example 1, and Experimental Example 3, and the epoxy resin portion of Experimental Example 1 and Experimental Example 3 was proved. The epoxy group has indeed been opened. Further, the resin compositions of Experimental Example 1 and Experimental Example 3 all had an amine-based characteristic peak (3416 cm ^-1 ) as shown in Fig. 2(b) - 2(c).

In addition, in order to understand the reaction state of the resin composition and the fluorine-based resin, the preliminary analysis of the resin composition of Experimental Example 1, the resin composition of Experimental Example 1, and the fluorine-based resin layer, and the fluorine-based resin layer were subjected to infrared spectrum identification. The results are shown in Figures 3(a)-3(c). As shown in Fig. 3(a), the resin composition of Experimental Example 1 has a characteristic peak of oxime-bonding (769, 691 cm ^-1 ) and a characteristic peak of epoxy group (914 cm ^-1 ). As shown in Fig. 3(b), when the resin composition of Experimental Example 1 was brought into contact with the fluorine-based resin layer, the characteristic peak of the epoxy group (914 cm ^-1 ) disappeared, and it was confirmed that the epoxy group had reacted with the hydroxyl group.

The obtained fluorine-based resin composite material was tested for 90° peel strength in accordance with the test specification ISO2411 (clamp spacing: 7.5 cm, test speed: 100 ± 10 mm/min). The peel strength test results of Comparative Examples 1-3 and Experimental Examples 1-3 are shown in Table 2.

As shown in Table 2, the peel strengths of Experimental Examples 1-3 were higher than those of Comparative Examples 1-3. Among them, the peel strength of Experimental Example 1 was the highest, and it was about 2.4 times of the peel strength of Comparative Example 1. From this, it was found that the resin composition of Experimental Example 1-3 can effectively form a chemical bond with the fluorine-based resin layer, and the adhesion strength between the fluorine-based resin layer and the polyester cloth can be improved.

In order to understand the inorganic cerium content of the adhesive layer, the adhesive layers of Experimental Example 1, Experimental Example 2, and Experimental Example 3 were subjected to EDX elemental analysis, as shown in Figures 4-6, wherein the horizontal axis of each graph is the excited signal. The energy (KeV), the vertical axis is the number of times the signal is received (counts). It can be seen from the above EDX element analysis that the content of the ruthenium element of the adhesive layer is between 1.03 and 2.37%.

Further, the adhesive layers of Experimental Example 1, Experimental Example 2, and Experimental Example 3 were subjected to a thermogravimetric loss test under a nitrogen atmosphere (heating rate 10 ° C / min) as shown in Fig. 7. At a temperature range of 200 to 400 ° C, mainly small molecule cleavage in the adhesive layer. At temperatures ranging from 400 to 470 ° C, mainly thermal cracking of the epoxy resin backbone segment. Importantly, with the amino polyoxyalkylene As the content increases, the rate of thermal cracking of the epoxy resin main chain section (at a temperature range of 400 to 470 ° C) becomes slow. The addition of an amine-based polyoxyalkylene does help to improve the thermal stability of the adhesive layer.

Further, the adhesive layers of Experimental Example 1, Experimental Example 2, and Experimental Example 3 were subjected to a thermogravimetric loss test in an air atmosphere (heating rate 10 ° C / min) as shown in Fig. 8. At a temperature range of 200 to 400 ° C, mainly small molecule cleavage in the adhesive layer. At temperatures ranging from 400 to 470 ° C, mainly thermal cracking of the epoxy resin backbone segment. At a temperature range of 500 to 650 ° C, it is mainly a thermal oxidative cracking of a helium oxygen structure. Further, at 700 ° C, the remaining weight percentage of the adhesive layer (that is, the content of inorganic cerium) is about 1 to 3%, which is similar to the result of EDX elemental analysis.

Comparative Example 4: Fluorine-based resin composite material without an adhesive layer (base material is glass fiber cloth)

In Comparative Example 4, a fluorine-based resin composite material was produced by the method described in Comparative Example 1, except that the base material of Comparative Example 4 was a glass fiber cloth.

Comparative Example 5: A fluorine-based resin composite material in which an adhesive layer is an epoxy resin (the base material is a glass fiber cloth)

In Comparative Example 5, a fluorine-based resin composite material was produced by the method described in Comparative Example 2, except that the base material of Comparative Example 5 was a glass fiber cloth.

Comparative Example 6: The adhesive layer was a fluorine-based resin composite of KBM-303 (the base material was a glass fiber cloth)

Comparative Example 6 was a method for preparing a fluorine-based resin composite by the method described in Comparative Example 3. The only difference was that the substrate of Comparative Example 6 was a glass fiber cloth.

Experimental Example 4-6: Fluorine-based resin composite material in which the adhesive layer was a resin composition (the base material was a glass fiber cloth)

Experimental Example 4-6 A fluorine-based resin composite material was prepared by the method described in Experimental Example 1-3, except that the substrate of Experimental Example 4-6 was a glass fiber cloth. That is, the resin compositions used in Experimental Examples 4, 5, and 6 were the same as Experimental Examples 1, 2, and 3, respectively.

The peel strength test results of Comparative Examples 4-6 and Experimental Examples 4-6 are shown in Table 3.

As shown in Table 2, the peel strengths of Experimental Examples 4 to 5 were higher than those of Comparative Examples 1-3. Among them, the peel strength of Experimental Example 4 was the highest, and it was about twice the peeling strength of Comparative Example 1. From this, it was found that the resin composition of Experimental Example 1-3 can effectively form a chemical bond with the fluorine-based resin layer, and the adhesion strength between the fluorine-based resin layer and the glass fiber cloth can be improved.

UV irradiation test

The fluorine-based resin composite material of Experimental Example 1 was subjected to an ultraviolet light irradiation test (i.e., a weather resistance test). As shown in Fig. 9, the left image (A) is the surface of the fluorine-based resin composite material that is not irradiated with ultraviolet light, and the right image (B) is the ultraviolet light for 7 days. The surface of the fluorine-based resin composite. Comparing the graphs (A) and (B), it was found that after 7 days of ultraviolet light irradiation, no significant change in color development or appearance was observed on the surface of the fluorine-based resin composite material, that is, after 7 days of irradiation with ultraviolet light, according to the present. The surface of the fluorine-based resin composite material of Experimental Example 1 of the invention did not exhibit yellowing or hardening.

Further, the fluorine-based resin composite material irradiated with ultraviolet light for 7 days was tested for 90° peel strength, and as a result, it was 36.36 N. The fluorine-based resin composite of Experimental Example 1 was able to maintain good adhesion even under the condition of irradiating ultraviolet light for 7 days.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

10‧‧‧Fluorine resin composite

110‧‧‧Substrate

120‧‧‧ adhesive layer

130‧‧‧Fluorinated resin layer

The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt;

Fig. 2 is an infrared spectrum chart showing the resin compositions of Comparative Example 2 (a), Experimental Example 1 (b), and Experimental Example 3 (c).

Fig. 3 is an infrared spectrum diagram showing the resin composition (a) of Experimental Example 1, the preliminary product (b) and the fluorine-based resin layer (c) after the resin composition was brought into contact with the fluorine-based resin layer.

Figures 4, 5 and 6 show experimental example 1, experimental example 2, and experiment respectively. Example 3 EDX element analysis chart.

Fig. 7 is a graph showing the thermogravimetric loss analysis (nitrogen atmosphere) of Comparative Example 2, Experimental Example 1, Experimental Example 2, and Experimental Example 3.

Fig. 8 is a graph showing the thermogravimetric loss analysis (air environment) of Comparative Example 2, Experimental Example 1, Experimental Example 2, and Experimental Example 3.

10‧‧‧Fluorine resin composite

110‧‧‧Substrate

120‧‧‧ adhesive layer

130‧‧‧Fluorinated resin layer

Claims (16)

A resin composition for a fluorine-based resin, comprising: an epoxy resin; and an amine polysiloxane, formed by a hydrolysis condensation reaction of an amino alkoxysilane with an aromatic alkoxysilane; The molar ratio of the resin composition to the epoxy group of the epoxy resin is from 0.06 to 0.77. The resin composition according to claim 1, wherein the molar ratio of the amino alkoxydecane to the aromatic alkoxydecane is 1/3 to 1/1. The resin composition according to claim 1, wherein the weight ratio of the amine polysiloxane to the epoxy resin is from 1:20 to 4.5:10. The resin composition according to claim 1, wherein the resin composition has an inorganic cerium content of 1.0 to 5.0% by weight. The resin composition according to claim 1, wherein the amino alkoxydecane has the formula H ₂ NR ³ -Si(R ² ) _a (OR ¹ ) _3-a , wherein R ¹ and R ² are H or C1-C4 alkyl, a is 0 or 1, R ³ is a C1-C10 alkyl group or R ⁵ -NH-R ⁴ , and R ⁴ and R ⁵ are a C1-C10 alkyl group. The resin composition according to claim 1, wherein the aromatic alkoxydecane has the formula R ⁸ -Si(R ⁷ ) _b (OR ⁶ ) _3-b , wherein R ⁶ and R ⁷ are H or C1- C4 alkyl, b is 0 or 1, and R ⁸ is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and combinations thereof. A method for producing a resin composition for a fluorine-based resin, comprising: mixing an amino alkoxydecane and an aromatic alkoxy decane to form an amine-based polyoxyalkylene; and mixing a ring An oxy resin and the amine polysiloxane are formed to form the resin composition, wherein a molar ratio of the resin composition to the epoxy group of the epoxy resin is from 0.06 to 0.77. The method of claim 7, wherein the molar ratio of the amino alkoxydecane to the aromatic alkoxydecane is 1/3 to 1/1. The method of claim 7, wherein the weight ratio of the amine polysiloxane to the epoxy resin is from 1:20 to 4.5:10. The method of claim 7, wherein the amino alkoxydecane has the formula H ₂ NR ³ -Si(R ² ) _a (OR ¹ ) _3-a , wherein R ¹ and R ² are H or C1- C4 alkyl, a is 0 or 1, R ³ is a C1-C10 alkyl group or R ⁵ -NH-R ⁴ , and R ⁴ and R ⁵ are a C1-C10 alkyl group. The method of claim 7, wherein the aromatic alkoxydecane has the formula R ⁸ -Si(R ⁷ ) _b (OR ⁶ ) _3-b , wherein R ⁶ and R ⁷ are H or a C1-C4 alkane The group, b is 0 or 1, and R ⁸ is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and combinations thereof. The method of claim 7, wherein the amino alkoxydecane is mixed with the aromatic alkoxy decane in an acidic environment. The method of claim 12, wherein the acidic environment has a pH of from 1 to 3. A method for producing a fluorine-based resin composite, comprising: providing a substrate; forming an adhesive layer on the substrate, wherein the adhesive layer comprises the resin composition according to any one of claims 1 to 6. And a fluorine-based resin layer having a hydroxyl group on the adhesive layer in an environment of 90 to 120 ° C. A fluorine-based resin composite material produced by the production method described in claim 14. The fluororesin composite according to claim 15, wherein the substrate comprises polyester, glass fiber or a combination thereof.