TWI515255B - Curable resin and curable composition using the same - Google Patents

Description

Curable resin and curable composition using the same

The present invention relates to a curable resin and a curable composition using the same, and more particularly to a curable resin having a plurality of crosslinking reactive groups and a curable composition using the same.

Optical components need to balance optical properties with physical properties, so a layer of anti-wear, scratch-resistant hardened protective coating must be applied to the outer layer. In general, photocurable resins are often used as surface protective coatings for photovoltaic, livelihood, IC, etc., because the curing speed of the photocurable resin is fast, which can effectively improve production efficiency while saving energy consumption and reducing the generation of organic volatile components.

However, generally, the photocurable resin having rigidity is an aromatic group molecule, and it is easy to cause a slight electron transfer due to temperature and time, and the composition is yellowed, resulting in poor temperature resistance and weather resistance. Long-term storage during processing or use and after product production is likely to affect the appearance and properties of the product due to yellowing, which in turn affects product quality.

The present invention relates to a curable resin having a plurality of crosslinking reactive groups and a curable composition using the same, comprising isocyanuric acid as a core structure, a plurality of branched substituent side chains, and a terminal crosslinking reaction Base, has good temperature and weather resistance, and is not prone to yellowing.

According to the present invention, a curable resin is proposed, which is represented by the chemical formula (1):

Wherein at least one of R1, R2 and R3 is R4 includes a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ alkenyl group, a C ₄ to C ₆ cycloalkyl group, and a C ₄ to C ₆ cycloolefin. A cycloalkenyl group or a phenyl group, R5 includes an acrylate derivatives, and the acrylate derivative includes at least two functional groups.

According to the present invention, a curable composition is provided comprising a photoinitiator and a curable resin. The content of the photoinitiator is 0.1 to 30% by weight, and the content of the curable resin is 1 to 99.7 wt%. The curable resin is represented by the chemical formula (1):

Wherein at least one of R1, R2 and R3 is R4 includes a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ alkenyl group, a C ₄ to C ₆ cycloalkyl group, and a C ₄ to C ₆ cycloolefin. A cycloalkenyl group or a phenyl group, R5 includes an acrylate derivatives, and the acrylate derivative includes at least two functional groups.

In order to provide a better understanding of the above and other aspects of the present invention, the following detailed description of the embodiments and the accompanying drawings

Fig. ^{1 is a 1} H NMR spectrum of a curable resin according to a second embodiment of the present invention.

The curable resin of the embodiment of the invention may be represented by the chemical formula (1):

Wherein at least one of R1, R2 and R3 is , R4 comprises a C ₁ to C ₄ alkyl group (alkyl group), C ₁ to C ₄ alkenyl group (alkenyl group), a cycloalkyl group (cycloalkyl group) C ₄ to C _6, and C ₄ to C ₆ ring of A cycloalkenyl group or a phenyl group, R5 comprises an acrylate derivatives, and the acrylate derivative comprises at least two functional groups.

In an embodiment, R1, R2 and R3 may further comprise or The functional group of the acrylate derivative may include an acrylate group or a methacrylate group. For example, R5 may include pentaerythritol triacrylate or dipentaerythritol pentaacrylate.

Hereinafter, the curable resin of the embodiment of the present invention is produced by the steps of the first embodiment and the second embodiment. It is to be understood that the embodiments are not intended to limit the invention. On the other hand, any structure conforming to the above chemical formula (1) can be used as the curable resin of the present invention, and the method of production is not limited to the following first embodiment and second embodiment.

First embodiment

Weighed 490.02 g (0.75 mol) of Pentaerythritol triacrylate (PET3A) and 126.67 g (0.75 mol) of Methtyl hexa hydrophthalic anhydride (4-MHHPA) in a 1 L round bottom reaction tank. 0.30 g (600 ppm) of the inhibitor monomethyl ether of hydroquinone (MEHQ) and 6.12 g of the catalyst Triphenyl phosphine (TPP) were added, and after stirring at 90 ° C for eight hours, the reaction was carried out until the acid value was constant. The temperature was lowered to about 70 ° C, and filtered through a Buchner funnel (G3) to obtain a transparent clear viscous material, 562.21 g, yield 91.2%. The chemical reaction formula (2) is as follows:

Next, 336.30 g (0.50 mol) of the synthesized pentaerythritol triacrylate derivative, 50.00 g (0.17 mol) of Triglycidyl Isocyanurate (TGIC) and the inhibitor hydroxyl group were weighed in a 1 L round bottom reaction tank. Monomethyl ether of hydroquinone (MEHQ) 0.50 g (1300 ppm), after stirring evenly, add catalyst triethylamine (TEA) 0.35 g (0.7 wt%) and stabilizer triphenyl Phosphite (Triphenyl Phosphite) , TPPI) 0.03 g (75 ppm), reacted at 95 ° C for 14 hours, sampled to measure the acid value ≦ 5 mg KOH / g, that is, the reaction is completed, the curable resin FH-01 of the first embodiment of the present invention is obtained, 368.00 g, yield 85.6%. The reaction formula is as follows: (3):

Second embodiment

178.74 g (0.49 mol) of pentaerythritol triacrylate (PET3A) and 126.67 g (0.49 mol) of succinic anhydride (SA) were weighed in a 1 L round bottom reaction tank, and then stabilizer IR-1010 was added. 0.222 g (0.06 wt%) and 3.668 g of catalyst triphenylphosphine (TPP) were sold by BASF AG (Badische Anilin-und Soda-Fabrik, BASF). After stirring at 90 ° C for eight hours, the reaction was carried out to acid. The price is constant. The temperature was lowered to about 70 ° C and filtered through a Buchner funnel (G3) to give a clear clear viscous 370.455 g, yield >99.9%. The chemical reaction formula (4) is as follows:

Next, 185.228 g (0.24 mol) of the synthesized pentaerythritol triacrylate derivative, 24.97 g (0.084 mol) of triglycidyl isocyanurate (TGIC), and the inhibitor p-hydroxyanisole were weighed in a 1 L round bottom reaction tank. (MEHQ) 0.26 g (1300 ppm), after stirring evenly, adding 6.22 g of catalyst triphenylphosphine (TPP), reacting at 95 ° C for 14 hours, sampling and measuring the acid value ≦ 5 mg KOH / g, that means the reaction is completed, the present The curable resin FH-02 of the second embodiment of the invention was 217.081 g, and the yield was 94.58%. The reaction formula is as follows: (6):

Fig. 1 is a view showing the ¹ H NMR spectrum obtained by dissolving the curable resin of the above example in a solvent (d ₆ -DMSO).

In the embodiment of the present invention, the curable resin of the above embodiment can be used to prepare a curable composition as a surface protective coating. The curable composition of the embodiment of the present invention may include a photoinitiator and a curable resin. The content of the photoinitiator is 0.1 to 30% by weight, and the content of the curable resin is 1 to 99.7 wt%. Similarly, the curable resin is represented by the chemical formula (1).

Wherein at least one of R1, R2 and R3 is , R4 comprises a C ₁ to C ₄ alkyl group (alkyl group), C ₁ to C ₄ alkenyl group (alkenyl group), a cycloalkyl group (cycloalkyl group) C ₄ to C _6, and C ₄ to C ₆ ring of A cycloalkenyl group or a phenyl group, R5 comprises an acrylate derivatives, and the acrylate derivative comprises at least two functional groups.

In an embodiment, R1, R2 and R3 may further comprise or The functional group of the acrylate derivative may include an acrylate group or a methacrylate group. For example, R5 may include pentaerythritol triacrylate or dipentaerythritol pentaacrylate.

The curable composition of the embodiment of the present invention may also include a diluent, a solvent and an auxiliary. The content of the diluent may be 0.1 to 60% by weight, the content of the solvent may be 0.1 to 60% by weight, and the content of the auxiliary agent may be 0.1 to 5% by weight. Here, the auxiliary agent can be, for example, a drying accelerator, a thickener, an emulsifier, an antifoaming agent, a leveling agent or a surfactant. In addition, the curable embodiment of the present invention After the composition is coated and hardened, the hardness may be between 5H and HB.

Hereinafter, the curable resin produced by the above examples is separately prepared with a photoinitiator 1 (manufactured by Hengqiao, product number: chemcure-73) and photoinitiator 2 (manufactured by Hengqiao, product number: chemcure). -BP), photoinitiator 3 (manufactured by Hengqiao, trade name: chemcure-481) and other oligomers 1 which can be crosslinked (Changxing Manufacturing, product number: DR-E750), thinner 1 (Changxing Manufacturing) , product number: EM265), thinner 2 (manufactured by Changxing, product number: EM235), thinner 3 (manufactured by double bond, product number: DPGDA), auxiliary agent (surfactant, manufactured by BYK, product number: BYK-333 The solvent (containing Ethyl acetate, EA, Isopropyl acetate, IPA, n-Butyl acetate, BA, Isobutyl acetate, IBA) is mixed and can be formulated into a curable composition as a surface protective coating.

The following table summarizes the ingredients of each of the formed compositions.

Thereafter, the prepared composition was applied by a doctor blade to an optical grade polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product No. A4300) to form a film having a thickness of 4 to 6 μm. After baking at 60 ° C for 2 minutes, baking at 80 ° C for 2 minutes, followed by ultraviolet light to harden the film, and measuring the viscosity with a rheometer Brookfield R/S-CC plus Rheometer, pencil hardness The tester (ASTM D3363-2005) measures the hardness and the b* value of the yellow-blue degree described in the LAB color space coordinates of the spectrophotometric metering light transmittance (550 nm) and the description color. The test results are shown in Table 2 below.

Table II

As can be seen from the above Table 2, the curable composition prepared by the curable resin FH-01 of the first embodiment of the present invention and the curable resin FH-02 of the second embodiment of the present invention has a transmittance of more than 91%. b* is less than 0.15 and hardness is up to 2H. That is, the curable composition made of the curable resin of the embodiment of the present invention can have both good hardness and workability.

The following is a comparison and comparison of other curable resins prepared by the first embodiment and the second embodiment with the existing commercial curable resin, and comparing the resin 1 (manufactured by Guojing, product number: GU7900Z), comparing Resin 2 (manufactured by Changxing, product number: 623A-80), comparative resin 3 (manufactured by Miwon special chemical, Korea, product number: SP1106), and photoinitiator 1 in different proportions (manufactured by Hengqiao, product number: chemcure- 73), photoinitiator 3 (manufactured by Hengqiao, product number: chemcure-481) and other crosslinkable diluent 3 (double bond manufacturing, product number: DPGDA), thinner 4 (manufactured by IGM, the Netherlands) No.: Photomer 4006), thinner 5 (manufactured by Guojing, product number: GM61P00), auxiliary agent (surfactant, manufactured by BYK, product number: BYK-333), solvent (including Methyl Ethyl Ketone, MEK, n-Butyl) Acetate, BA, Isobutyl acetate, IBA) can be formulated into a curable composition as a surface protective coating.

The following Table 3 summarizes the ingredients of each of the formed compositions.

The prepared composition was respectively applied by a doctor blade on a poly(methyl methacrylate) (PMMA) block (provided by Zhuowei Optoelectronics, electronic grade) to form a film having a thickness of 3-6 μm. After baking at 60 ° C for 2 minutes, and then baking at 80 ° C for 2 minutes, then ultraviolet light is irradiated to harden the film, and the energy required for curing is judged by the dry touch (UV curing energy (mJ/cm). ² )), and pencil hardness, light transmittance (550 nm), b* value, and cotton-resistant rubbing test (load 1 kg, wipe 100 times without scratches), the results are shown in Table 4 below.

Table 4

As can be seen from the above Table 4, the curable composition prepared by the curable resin FH-01 of the first embodiment of the present invention and the curable resin FH-02 of the second embodiment of the present invention is coated on the PMMA and penetrated. The rate is greater than 90%, b* is less than 0.39, the hardness can reach 4H and can resist the friction of cotton cloth. Compared with the conventional commercial curable resin of the comparative example, it has low curing energy, good hardness, abrasion resistance and optical properties.

The prepared composition 8 and the conventional commercial curable resin (Comparative Examples 1 and 3) were respectively coated on a glass slide (FET microscope slides) to form a film having a thickness of 3 to 6 μm and at 60 ° C. After baking for 2 minutes, it was baked at 80 ° C for 2 minutes, and then ultraviolet light was irradiated to harden the film, and the yellowing resistance test was carried out by Atlas UVTest Fluorescent UV Condensation Weathering Device. The results are shown in Table 5 below.

As can be seen from the above Table 5, the curable composition prepared by the curable resin of the embodiment of the present invention has a Δb of only 0.09 after being irradiated for 1000 hours by the QUV, and has good yellowing resistance.

In conclusion, the present invention has been disclosed in the above embodiments, but it is not intended to limit the present invention. A person skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. because Therefore, the scope of the present invention is defined by the scope of the appended claims.

Claims (10)

A curable resin represented by the chemical formula (1): Wherein at least one of R1, R2 and R3 is R4 includes a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ alkenyl group, a C ₄ to C ₆ cycloalkyl group, a C ₄ to C ₆ cycloalkenyl group or a phenyl group, and R 5 includes an acrylate derivative. The acrylate derivative includes at least two functional groups. The curable resin according to claim 1, wherein the R1, R2 and R3 further comprise or The curable resin of claim 1, wherein the at least two functional groups comprise an acrylate group or a methacrylate group. The curable resin according to claim 1, wherein the R5 package Including pentaerythritol triacrylate or dipentaerythritol pentaacrylate. A curable composition comprising: a photoinitiator in an amount of 0.1 to 30% by weight; and a curable resin in an amount of 1 to 99.7 wt%, the curable resin being represented by the chemical formula (1): Wherein at least one of R1, R2 and R3 is R4 includes a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ alkenyl group, a C ₄ to C ₆ cycloalkyl group, a C ₄ to C ₆ cycloalkenyl group or a phenyl group, and R 5 includes an acrylate derivative. The acrylate derivative includes at least two functional groups. The curable composition according to claim 5, further comprising: a diluent in an amount of 0.1 to 60% by weight; and a solvent in an amount of 0.1 to 60% by weight. The curable composition according to claim 5, wherein the curable composition has a hardness of between 5H and HB after being coated and hardened. The curable composition of claim 5, wherein the R1, R2 and R3 are further included or The curable composition of claim 5, wherein the at least two functional groups comprise an acrylate group or a methacrylate group. The curable composition of claim 5, wherein the R5 comprises a pentaerythritol triacrylate group or a dipentaerythritol pentaacrylate group.