TWI631096B - Cation surfactant, method of producing the same and application thereof - Google Patents

Abstract

The present invention relates to a cationic surfactant as shown in formula (I):

R ₁ is an alkyl group having 1 to 30 carbon atoms, an olefin group having 2 to 30 carbon atoms or a cycloalkane group having 3 to 30 carbon atoms; R ₂ is an alkyl group or alkyl alcohol group having 1 to 4 carbon atoms , Alkylsulfonyl or alkylphenyl; R ₃ is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, an aromatic group, and an alkyl aromatic group , Alkenyl aromatic group or -OR ₄ ; R ₄ is an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, aromatic group, alkyl aromatic group, alkenyl aromatic group or ; R ₅ is an alkenyl group having 2 to 5 carbon atoms; at least one of R ₁ , R ₂ and R ₃ has an unsaturated group; Y ₁ and Y ₂ each represent an alkylene group having 2 to 4 carbon atoms; A ^- is an anionic hydrophilic group; and n and m each represent an integer of 0 to 100.

Description

Cationic surfactant, its manufacturing method and application

The invention relates to a cationic surfactant, in particular to a cationic surfactant which can improve antistatic property and antifog property, a method for manufacturing the same and application thereof.

With the emphasis on the quality of life, the known electronic products are becoming thinner and lighter, and the optoelectronic components inside the electronic products are increasingly miniaturized. However, as the volume of photovoltaic elements shrinks, the requirements for the use environment become more stringent.

When optoelectronic components are used in high-temperature and high-humidity environments, the mist is easy to condense on the surface of the component, which affects its performance and even causes component damage. In particular, in the display field, fog will affect the display of the display and reduce its performance.

Secondly, since the optoelectronic element mainly promotes its effect through the conduction of charge, a stable electric field environment helps to improve the performance of the optoelectronic element. However, the static electricity generated in daily life often affects photovoltaic devices. Although static is transient Discharge, but it has a high voltage, so static electricity often causes great damage to miniaturized photovoltaic elements.

In order to effectively eliminate the damage caused by the fog or static electricity to the photovoltaic element, the surface of the photovoltaic element can be provided with an anti-fog material or an anti-static material to prevent the fog from condensing or eliminating static electricity, thereby preventing damage to the photovoltaic element.

The aforementioned anti-fogging material or anti-static material may generally be a composite film containing a surfactant (such as an anti-fogging agent or an anti-static agent) to have the aforementioned effects.

However, the conventional anti-fogging agent or antistatic agent is only physically mixed with the resin material of the protective film uniformly, so as the ambient temperature and humidity change or the time increases, the anti-fogging agent or antistatic agent will migrate. To the surface of the composite film, and reduce its anti-fogging or antistatic performance.

Secondly, the anti-fog or anti-static agent migrated to the surface will also cause after-tack on the surface of the composite film, and reduce its surface properties.

In view of this, there is an urgent need to provide a cationic surfactant, a method for manufacturing the same, and an application thereof in order to improve the drawbacks of the conventional cationic surfactant, the method for manufacturing the same, and its application.

Therefore, one aspect of the present invention is to provide a cationic surfactant. By selecting a reactant, a cationic surfactant having a specific structure and having good antistatic and antifogging properties is prepared.

Another aspect of the present invention is to provide a method for manufacturing a cationic surfactant, and the prepared cationic surfactant has the aforementioned specific structure.

Another aspect of the present invention is to provide a photocurable resin composition including the aforementioned cationic surfactant.

Another aspect of the present invention is to provide a composite film including a photo-curable film prepared by using the aforementioned photo-curable resin composition.

According to one aspect of the present invention, a cationic surfactant is proposed, and has a structure represented by the following formula (I):

In formula (I), R ₁ represents an alkyl group having 1 to 30 carbon atoms, an olefin group having 2 to 30 carbon atoms or a cycloalkane group having 3 to 30 carbon atoms; R ₂ represents an alkyl group having 1 to 4 carbon atoms Alkyl, alkylalcohol, alkanoyl or alkylphenyl; R ₃ represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, Aryl, alkylaryl, alkenylaryl or -OR ₄ ; R ₄ represents alkenyl having 2 to 5 carbons, alkynyl having 2 to 5 carbons, aromatic, alkylaryl, alkenyl Aromatic or ; R ₅ represents an alkenyl group having 2 to 5 carbon atoms; at least one of R ₁ , R ₂ and R ₃ has an unsaturated group; Y ₁ and Y ₂ each independently represent an alkylene group having 2 to 4 carbon atoms A ^- is an anionic hydrophilic group; and n and m each independently represent an integer from 0 to 100.

One embodiment according to the present invention, examples of the anionic hydrophilic group comprising ^{F -, Cl -, Br -} , I -, (SO 2 CF 3) 2 N - or And R ₆ represents methyl or ethyl.

According to another aspect of the present invention, a method for manufacturing a cationic surfactant is proposed. In this method, a pre-reaction is first performed on a mixture to form an intermediate product. The pre-reaction includes a first reaction, and the mixture includes an amine compound represented by the following formula (I-1) and the following formula (I-2) The epoxy compound shown: R ₁ -NH ₂ (I-1)

In the formula (I-1), R ₁ represents an alkyl group having 1 to 30 carbon atoms, an olefin group having 2 to 30 carbon atoms or a cycloalkane group having 3 to 30 carbon atoms;

In formula (I-2), R ₃ represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, an aromatic group, an alkyl aromatic group, Alkenyl aryl or -OR ₄ ; R ₄ represents alkenyl having 2 to 5 carbon atoms, alkynyl having 2 to 5 carbon atoms, aromatic group, alkyl aromatic group, alkenyl aromatic group, or And R ₅ represents an alkenyl group having 2 to 5 carbon atoms.

Then, a quaternary reaction is performed on the obtained intermediate product and the compound represented by the following formula (I-3) to obtain a cationic surfactant. The cationic surfactant has the aforementioned structure, and n and m each represent 0: R ₂ -A (I-3)

In the formula (I-3), R ₂ represents an alkyl group, an alkyl alcohol group, an alkyl fluorenyl group, or an alkyl phenyl group having a carbon number of 1 to 4; and A is a hydrophilic group.

According to an embodiment of the present invention, after performing the aforementioned first reaction, the pre-reaction further includes performing a second reaction on a product of the first reaction and an alkylene oxide compound having a carbon number of 2 to 4.

According to another embodiment of the present invention, the cationic surfactant prepared by the aforementioned manufacturing method has the aforementioned structure, wherein n and m respectively represent integers from 0 to 100, and the sum of n and m is greater than 0.

According to another embodiment of the present invention, the aforementioned hydrophilic group includes a halogen atom, (SO ₂ CF ₃ ) ₂ N- or , R ₆ represents methyl or ethyl, and "*" represents a bonding position.

According to another aspect of the present invention, a photocurable resin composition is provided. The photocurable resin composition includes a photocurable resin material and the aforementioned cationic surfactant. Among them, based on the use amount of the photocurable resin material is 100 parts by weight, and the use amount of the cationic surfactant is 0.5 to 30 parts by weight.

According to another aspect of the present invention, a composite film is proposed. The composite film includes a substrate and a photo-curable film, and the photo-curable film is disposed on the surface of the substrate. The photo-curable film is formed by the aforementioned photo-curable resin composition through a photo-curing process. The contact angle to water does not exceed 50 degrees.

According to an embodiment of the present invention, the first impedance value of the aforementioned composite film per unit area is less than 10 ¹¹ ohms.

According to another embodiment of the present invention, after the aforementioned composite film is placed in a high temperature and high humidity environment, the second impedance value of the composite film per unit area is less than 10 ¹¹ ohms, and the ratio of the second impedance value to the first impedance value Department is less than 50 and greater than 0.

The cationic surfactant of the present invention, its manufacturing method, and its application have good time stability by forming a chemical bond between the unsaturated group of the cationic surfactant and the resin material.

100‧‧‧ Method

110‧‧‧Procedure for providing a mixture

120‧‧‧ Pre-reaction step

130‧‧‧ Steps to perform quaternization reaction

140‧‧‧ Steps to prepare cationic surfactant

In order to have a more complete understanding of the embodiments of the present invention and its advantages, please refer to the following description and cooperate with the corresponding drawings. It must be emphasized that the various features are not drawn to scale and are for illustration purposes only. The contents of the related drawings are described as follows: [FIG. 1] A flowchart showing a method for manufacturing a cationic surfactant according to an embodiment of the present invention.

The manufacture and use of the embodiments of the invention are discussed in detail below. It is understood, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific content. The specific embodiments discussed are for illustration only and are not intended to limit the scope of the invention.

The term “after-tack” in the present invention refers to the surface adhesion defect caused by the temperature and humidity of the coating film or the migration of the anti-fog or antistatic agent to the surface of the composite film, which makes the surface of the coating film easy. Contamination sticks, or reduces the surface flatness, thereby reducing the surface properties of the coating film.

Please refer to FIG. 1, which is a flowchart illustrating a method for manufacturing a cationic surfactant according to an embodiment of the present invention. In one embodiment, the manufacturing method first provides a mixture, as shown in step 110. This mixture contains an amine compound represented by the following formula (I-1) and an epoxy compound represented by the following formula (I-2): R ₁ -NH ₂ (I-1)

In the formula (I-1), R ₁ represents an alkyl group having 1 to 30 carbon atoms, an olefin group having 2 to 30 carbon atoms or a cycloalkane group having 3 to 30 carbon atoms.

In the formula (I-1), R ₁ may be a substituted or unsubstituted straight chain group or a branched chain group. In an embodiment, when R ₁ represents an alkyl group having 1 to 30 carbon atoms, R ₁ may include, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl , Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecane Base, eicosyl, behenyl, behenyl, behenyl, behenyl, behenyl, behenyl, isopentyl, isohexyl, isoheptyl, isooctyl Isoyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isohexadecyl Base, isooctadecyl, ethylhexyl, ethylheptyl, ethyloctyl, ethylnonyl, ethyldecyl, propylhexyl, propylheptyl, propyloctyl, propylnonyl Propyldecyl, butylhexyl, butylheptyl, butyloctyl, butylnonyl, butyldecyl, secondary hexyl, secondary heptyl, secondary octyl, secondary nonyl, secondary decyl, Secondary undecyl, secondary dodecyl, secondary tridecyl, di Tetradecyl, secondary pentadecyl or secondary hexadecyl and the like. When R ₁ represents an olefin group having a carbon number of 2 to 30, R ₁ may include, but is not limited to, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decyl Alkenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptenyl, or octadecenyl, and the like. When R ₁ represents a cycloalkane group having a carbon number of 3 to 30, R ₁ may include, but is not limited to, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentylmethyl, cyclopentylethyl, Cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, cycloheptylmethyl, cycloheptylethyl, cycloheptylpropyl, Cycloheptylbutyl, cyclooctylmethyl, cyclooctylethyl, cyclooctylpropyl or cyclooctylbutyl and the like.

Preferably, R ₁ may represent an alkyl group having 6 to 25 carbons, an olefin group having 6 to 25 carbons, or a cycloalkane group having 6 to 25 carbons. The above-mentioned amine-based compounds represented by the formula (I-1) may be used alone or in combination.

In formula (I-2), R ₃ represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, an aromatic group, an alkyl aromatic group, Alkenyl aryl or -OR ₄ ; R ₄ represents alkenyl having 2 to 5 carbon atoms, alkynyl having 2 to 5 carbon atoms, aromatic group, alkyl aromatic group, alkenyl aromatic group, or And R ₅ represents an alkenyl group having 2 to 5 carbon atoms.

In the formula (I-2), R ₃ may be a substituted or unsubstituted linear group or a branched group. In an embodiment, specific examples of R ₃ may preferably include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, vinyl, and propenyl. , Butenyl, pentenyl, ethynyl, propynyl, butynyl, pentynyl, phenyl, benzyl, phenethyl, phenylpropyl, naphthyl, naphthylmethyl, naphthylethyl, Naphthyl, biphenyl, styryl, styryl, or methylstyryl. The epoxy compound represented by the formula (I-2) may be used singly or in combination.

Then, the aforementioned mixture is pre-reacted to form an intermediate product, as shown in step 120. The pre-reaction may include a first reaction, and the prepared intermediate product has a structure represented by the following formula (I-4-1):

In the formula (I-4-1), the definitions of R ₁ and R ₃ are as described above, and are not repeated here.

Based on the total usage of the amine compound represented by formula (I-1) is 1 mole, and the usage amount of the epoxy compound represented by formula (I-2) can be 0.5 mole Ears to 4.0 moles, preferably 1.0 to 3.0 moles, and more preferably 1.5 to 2.5 moles.

In one embodiment, the reaction temperature of the first reaction may be 70 ° C to 150 ° C, preferably 80 ° C to 140 ° C, and more preferably 90 ° C to 120 ° C. The reaction time of the first reaction may be 2 hours to 8 hours, preferably 2 hours to 6 hours, and more preferably 3 hours to 5 hours.

After step 120 is performed, a quaternary reaction is performed on the aforementioned intermediate product with a compound represented by the following formula (I-3), and a cationic surfactant represented by the following formula (I'-1) can be obtained, such as Steps 130 and 140 are shown.

R ₂ -A (I-3)

In the formula (I-3), R ₂ represents an alkyl group, an alkyl alcohol group, an alkyl fluorenyl group, or an alkyl phenyl group having a carbon number of 1 to 4; and A is a hydrophilic group.

In formula (I-3), R ₂ may be a substituted or unsubstituted straight-chain group or a branched-chain group. In an embodiment, when R ₂ represents an alkyl group having 1 to 4 carbon atoms, R ₂ may include, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tertiary Butyl. When R ₂ represents an alkyl alcohol group, R ₂ may include, but is not limited to, a methanol group, an ethanol group, a propanol group, a butanol group, an isopropanol group, an isobutanol group, and the like. When R ₂ represents an alkylfluorenyl group, R ₂ may include, but is not limited to, an ethylfluorenyl group, a propionyl group, a butanyl group, and the like. When R ₂ represents an alkylphenyl group, the alkyl group bonded to the phenyl group may be a linear or branched alkyl group having 1 to 3 carbon atoms, and R ₂ may include, but is not limited to, benzyl and benzene. Ethyl, phenylpropyl or phenylbutyl.

The hydrophilic group in the formula (I-3) may include, but is not limited to, a halogen atom, (SO ₂ CF ₃ ) ₂ N-, (R ₆ represents a methyl group or an ethyl group, and "*" represents a bonding position), other appropriate hydrophilic groups, or any combination thereof. Preferably, in the subsequent quaternization reaction, the hydrophilic group can react to form an anionic hydrophilic group. In one embodiment, the halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

When the aforementioned quaternization reaction is performed, the -R ₂ group of the compound represented by the formula (I-3) will be bonded with the nitrogen atom of the intermediate product to generate a quaternary ammonium salt, thereby preparing the present invention. A cationic surfactant.

In one embodiment, the total amount of the intermediate product used is 1 mol, and the amount of the compound represented by formula (I-3) may be 0.3 mol to 2.0 mol, preferably 0.5 mol to 1.5 mol, and more preferably 0.6 mol to 1.2 mol.

The reaction temperature of the aforementioned quaternization reaction may be 40 ° C to 90 ° C, preferably 50 ° C to 80 ° C, and more preferably 60 ° C to 70 ° C. The reaction time of the quaternization reaction may be 1 hour to 5 hours, preferably 1.5 hours to 4.5 hours, and more preferably 2 hours to 4 hours.

In formula (I'-1), the definitions of R ₁ , R ₂ and R ₃ are as described above, and are not repeated here. A ^- is an anionic hydrophilic group. Among them, at least one of R ₁ , R ₂ and R ₃ has an unsaturated group.

In one embodiment, the foregoing pre-reaction may optionally include a step of performing a second reaction between the product of the first reaction and the alkylene oxide compound having 2 to 4 carbon atoms to obtain a formula having the following formula (I -4-2) The intermediate product of the structure shown:

In the formula (I-4-2), the definitions of R ₁ and R ₃ are as described above, and are not repeated here; Y ₁ and Y ₂ each independently represent an alkylene group having a carbon number of 2 to 4; n and m represent integers from 0 to 100, and the sum of n and m is greater than 0.

In an embodiment, n and m may preferably independently represent integers from 0 to 50, and more preferably may independently represent integers from 0 to 30.

When the sum of n and m is greater than 0, the -OY ₁ -and / or -OY ₂ -segment can make the prepared cationic surfactant have the effects of hydrophilicity, anti-fogging property and antistatic property.

The sum of n and m may preferably be 5 to 50, and the sum of n and m may be more preferably 5 to 30.

When the sum of n and m is 5 to 30, the prepared cationic surfactant has better hydrophilicity, anti-fogging property and antistatic property.

Based on the total usage of the product of the first reaction is 1 mole, the usage of the aforementioned alkylene oxide compound having 2 to 4 carbons may be 2.0 to 50.0 moles, preferably 5.0 to 40.0 moles. Ears, and more preferably 5.0 to 30.0 moles.

In this embodiment, the intermediate product obtained as shown in the formula (I-4-2) can be further quaternized with the compound shown in the formula (I-3) to obtain the following: Cationic surfactant represented by formula (I'-2):

In the formula (I'-2) _{of, R 1, R 2, R} 3, Y 1, Y 2, A -, n and m have the previously described are, this is not described herein. Among them, at least one of R ₁ , R ₂ and R ₃ has an unsaturated group.

Similarly, when the quaternization reaction is performed, the -R ₂ group of the compound represented by the formula (I-3) will be bonded with the nitrogen atom of the intermediate product to generate a quaternary ammonium salt, thereby preparing the present compound. Invention of a cationic surfactant.

Wherein, based on the total amount of the intermediate product represented by the formula (I-4-2) being 1 mole, the amount of the compound represented by the formula (I-3) may be 0.3 mole to 2.0 mole, It is preferably from 0.5 mol to 1.5 mol, and more preferably from 0.6 mol to 1.2 mol.

In this embodiment, the reaction parameters (such as reaction temperature and reaction time) of the quaternization reaction may be the same as or different from the reaction parameters of the quaternization reaction described in step 130 above.

According to the foregoing description, the cationic surfactant prepared by the manufacturing method of the present invention has a structure represented by the following formula (I):

In formula (I), the definitions of R ₁ , R ₂ , R ₃ , Y ₁ , Y _2, and A ^- are as described above, and are not repeated here; and n and m each independently represent 0 to 100. Integer. Similarly, at least one of R ₁ , R ₂ and R ₃ has an unsaturated group.

In a specific example, the cationic surfactant of the present invention is mixed with a photocurable resin material to obtain a photocurable resin composition. Among them, based on the use amount of the photocurable resin material being 100 parts by weight, the use amount of the cationic surfactant may be 0.5 to 30 parts by weight, preferably 2.5 to 25 parts by weight, and more preferably 5 Part by weight to 20 parts by weight.

When the cationic surfactant is used in an amount of more than 30 parts by weight, the resulting photo-curable resin composition is liable to cause a defect of sticking back after film formation. When the amount of the cationic surfactant is less than 0.5 parts by weight, an excessively small amount of the cationic surfactant cannot effectively improve the performance of the photocurable resin composition.

In this specific example, when the aforementioned photocurable resin composition is irradiated with ultraviolet light or other energy rays, the double bond group in the photocurable resin material undergoes an addition polymerization reaction, and the cationic surfactant has a double bond The group [that is, R ₁ , R ₂ or R ₃ having an unsaturated group in the aforementioned formula (I)] will also participate in the addition polymerization reaction of the photocurable resin material, so that the cationic surfactant and the photoactive The cured resin material forms a chemical bond, which improves its stability over time.

In another specific example, the aforementioned photo-curable resin composition can be coated on a surface of a substrate, and a photo-curable film is formed by a photo-curing process to form a composite film. The first impedance value of the composite film per unit area is less than 10 ¹¹ ohms. Therefore, the prepared composite film can have good antistatic properties.

In this specific example, the aforementioned substrate may include, but is not limited to, optical films, glass substrates, plastic substrates, paper substrates, wood substrates, solar photovoltaic panels, other appropriate substrates, or any combination of the foregoing substrates. .

Secondly, because the cationic surfactant has a cationic hydrophilic group, the light-cured film produced has better anti-fogging properties, and can improve the anti-fogging properties of the composite film. In one embodiment, the contact angle of the light-cured film of this case to water is not more than 50 degrees, preferably not more than 35 degrees, and more preferably not more than 20 degrees. When the contact angle of the photo-cured film with water exceeds (ie, is greater than) 50 degrees, the anti-fogging property of the photo-cured film decreases.

According to the foregoing description, it can be known that when the photocurable resin composition of the present invention undergoes a photocuring process, the unsaturated groups of R ₁ , R ₂ or R ₃ in the cationic surfactant shown in formula (I) will interact with The double bond group of the photo-curable resin material forms an addition polymerization reaction, which results in chemical bonding, thereby having better stability over time.

Therefore, when the composite film of the present invention is placed in a high-temperature and high-humidity environment for a long time, the resistance value of the composite film can still be less than 10 ¹¹ ohms, the static electricity change is also less than 50 and greater than 0, and it has good anti-fog properties. Accordingly, the cationic surfactant of the present invention has good stability over time.

Preferably, the aforementioned electrostatic change is less than 10 and greater than or equal to 0.1; more preferably, the aforementioned electrostatic change is less than or equal to 5 and greater than or equal to 0.1.

In another embodiment, when the composite film of the present invention is placed in a high temperature and high humidity environment for a long time, the resistance value of the composite film may be smaller than the resistance value of the composite film before being placed. The reason is that after being affected by the high temperature and high humidity environment for a long time, the composite film will absorb the moisture in the environment, and the impedance value in the composite film will be reduced.

In an application example, the photocurable resin composition of the present invention can be applied to any substrate in addition to the coating industry, so that it has good antistatic properties and antifogging properties.

The following uses examples to illustrate the application of the present invention, but it is not intended to limit the present invention. Any person skilled in the art can make various changes and decorations without departing from the spirit and scope of the present invention.

Preparation of photocurable resin material Preparation example R-1

First, 55 to 65 parts by weight of an aliphatic urethane diacrylate (made by Changxing Material Industry Co., Ltd., trade name 611B-85), and 9 to 16 parts by weight of ethoxylation Trimethylolpropane triacrylate (Ethoxylated trimethylolpropane triacrylate; manufactured by Satomer, trade name SR415), 25-35 parts by weight of 2- (2-ethoxyethoxy) ethyl acrylate [2- ( 2-Ethoxyethoxy) ethyl acrylate; manufactured by Satomer, trade name SR256], 0 to 5 parts by weight of tetrahydrofurfuryl acrylate (Tetrahydrofurfuryl acrylate; manufactured by Changxing Materials Industry Co., Ltd., trade name EM214), 1 part by weight To 5 parts by weight of 1-Hydroxycyclohexyl phenyl ketone (1-Hydroxycyclohexyl phenyl ketone; photoinitiator; manufactured by BASF, trade name Irgacure 184) and 1 to 2 parts by weight of 2,4,6 -Trimethylbenzyl-diphenylphosphine oxide [Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide; photoinitiator; manufactured by BASF, trade name Darocur TPO], and added to the mixer, and At room temperature , Stirring continued stirring and mixing means, can be prepared R-1 Preparation of photocurable resin material.

Preparation example R-2

First, 15 to 25 parts by weight of Bisphenol A epoxy diacrylate (Sartomer Corporation, trade name CN 104), 20 to 30 parts by weight of 2-phenoxyethyl Acrylate (2-Phenoxyethyl acrylate; manufactured by Satomer, trade name SR 339), 15 to 25 parts by weight of ethoxy Ethoxylated bisphenol A diacrylate (Satomer, trade name SR 349), 20 to 30 parts by weight of o-Phenyl phenoxy ethyl acrylate; Changxing Made by Materials Industry Co., Ltd. and its trade name is EM2105], 4 to 5 parts by weight of 1-Hydroxycyclohexyl phenyl ketone (1-Hydroxycyclohexyl phenyl ketone; photoinitiator; BASF company, trade name Irgacure 184) and 1 to 2 parts by weight of 2,4,6-trimethylbenzyl-diphenylphosphine oxide [Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide; photoinitiator ; Manufactured by BASF company, trade name Darocur TPO] was added to the mixer, and continuously stirred and mixed with a stirring device at room temperature to prepare a photocurable resin material of Preparation Example R-2.

Preparation example R-3

First, 30 to 40 parts by weight of 2-Phenoxyethyl acrylate (manufactured by Satomer, trade name SR 339), 15 to 25 parts by weight of 1,6-hexane Ethoxylated bisphenol A diacrylate (1,6-hexanediol diacrylate; trade name SR 238, manufactured by Satomer); 25 to 35 parts by weight of ethoxylated bisphenol A diacrylate; Satomer Manufactured under the trade name SR 349), 20 parts by weight to 30 parts by weight of Tripropylene glycol diacrylate (manufactured by Synergy Technology Co., Ltd. and its trade name is 2815), 3 parts by weight to 5 parts by weight 1-Hydroxycyclohexyl phenyl ketone (1-Hydroxycyclohexyl phenyl ketone; photoinitiator; Manufactured by BASF Corporation under the trade name Irgacure 184) and 1 to 2 parts by weight of 2,4,6-trimethylbenzylidene-diphenylphosphine oxide [Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide; photoinitiator; manufactured by BASF, trade name Darocur TPO], added to the mixer, and continuously stirred and mixed with a stirring device at room temperature to prepare a photocurable resin of Preparation Example R-3 material.

Preparation of cationic surfactant Production Example S-1

First, 1 mol (129 g) of 2-ethylhexylamine and 2 mol (228 g) of propylene glycidyl ether were added to a reaction flask, and the temperature was raised to 100 ° C to 120 ° C to perform a first reaction. After 3 hours of reaction, 5 mol (220 g) of ethylene oxide was introduced, and the temperature was raised to 150 ° C. to perform a second reaction. After aging for 2 hours, the intermediate product of Preparation Example S-1 was obtained. Next, 1 mol (92 g) of 1-chlorobutane was dropped into the aforementioned intermediate product, and the temperature was adjusted to 100 ° C. to perform a quaternization reaction. After 8 hours of reaction, the cationic surfactant (where n + m = 5) of Preparation Example S-1 shown in the following formula (II-1) can be obtained:

Preparation Example S-2

1 mole (186 g) of dodecylamine and 2 mole (228 g) of propenyl glycidyl ether were added to the reaction flask, and the temperature was raised to 100 ° C to 120 ° C to perform the first reaction. After 3 hours of reaction, 10 mol (440 g) of ethylene oxide was introduced, and the temperature was raised to 150 ° C. to perform a second reaction. After aging for 2 hours, the intermediate product of Preparation Example S-2 was obtained. Next, 1 mol (154 g) of diethyl sulfate was dropped into the aforementioned intermediate product, and a quaternization reaction was performed at 50 ° C. After 2 hours of reaction, the following formula (II-2) was obtained: The cationic surfactant of Preparation Example S-2 is shown (where n + m = 10):

Preparation Example S-3

1 mole (269 g) of octadecylamine and 2 mole (228 g) of propylene glycidyl ether were added to the reaction flask, and the temperature was raised to 100 ° C to 120 ° C to perform the first reaction. After 3 hours of reaction, 30 mol (1320 g) of ethylene oxide was introduced, and the temperature was raised to 150 ° C. to perform a second reaction. After ripening for 2 hours, the intermediate product of Preparation Example S-3 was obtained. Next, 1 mole (126 g) of dimethyl sulfate was dropped into the aforementioned intermediate product, and a quaternization reaction was performed at 50 ° C. After 2 hours of reaction, the cationic surfactant (where n + m = 30) of Preparation Example S-3 shown in the following formula (II-3) can be obtained:

Preparation Example S-4

1 mole (99 g) of cyclohexylamine and 2 mole (228 g) of propylene glycidyl ether were added to the reaction bottle, and the temperature was raised to 100 ° C to 120 ° C to perform the first reaction. After 3 hours of reaction, 20 mol (880 g) of ethylene oxide was introduced, and the temperature was raised to 150 ° C. to perform the second reaction. After ripening for 2 hours, the intermediate product of Preparation Example S-4 was obtained. Next, 1 mol (126 g) of benzyl chloride was dropped into the aforementioned intermediate product, and a quaternization reaction was performed at 80 ° C. After 8 hours of reaction, the following formula (II-4) was obtained: Cationic surfactant of Preparation Example S-4 (where n + m = 20):

Preparation Example S-5

1 mol (157 g) of isodecylamine and 2 mol (228 g) of propylene glycidyl ether were added to the reaction flask, and the temperature was raised to 100 ° C to 120 ° C to perform the first reaction. After 3 hours of reaction, the intermediate product of Preparation Example S-5 was obtained. Next, 1 mol (126 g) of dimethyl sulfate was dropped into the aforementioned intermediate product, and a quaternization reaction was performed at 50 ° C. After 2 hours of reaction, the following formula (II-5) was obtained: Cationic surfactant of Preparation Example S-5:

Preparation of composite film

The following are the composite films of Examples 1 to 17 and Comparative Examples 1 to 9 based on Tables 1 and 2.

Example 1

100 parts by weight of a photocurable resin material (Preparation Example R-1) and 10 parts by weight of a cationic surfactant (Preparation Example S-1) were added to a mixer, and continued at a room temperature with a stirring device The photo-curable resin composition of Example 1 can be obtained by stirring and mixing.

Then, the aforementioned photocurable resin composition is coated on a substrate and irradiated with ultraviolet light to form a photocurable film, and the composite film of Example 1 can be obtained. The obtained composite film was evaluated by the following evaluation methods such as surface properties, adhesiveness, antistatic property, anti-fog property, and environmental test. The results are shown in Table 1.

Examples 2 to 17 and Comparative Examples 1 to 9

Examples 2 to 17 and Comparative Examples 1 to 9 use the same preparation method as the method for manufacturing the composite film of Example 1, except that Examples 2 to 17 and Comparative Examples 1 to 9 change the photo-curable film. The types and amounts of photo-curable resin materials and cationic surfactants, and the evaluation results are shown in Tables 1 and 2, respectively, and will not be repeated here.

Evaluation item Surface property

The photocurable resin compositions prepared in the foregoing Examples 1 to 17 and Comparative Examples 1 to 9 were evenly coated on a PET film with a # 4 coating rod to form a coating film having a thickness of 10 μm. Touch the light-cured film with a hand to determine whether it is dry, and evaluate it on the following criteria: ○: The surface is completely dry; △: The surface is not completely dry; 干燥: The surface is tacky.

2. Appearance

The photocurable resin compositions prepared in the foregoing Examples 1 to 17 and Comparative Examples 1 to 9 were coated on a substrate having a specific pattern. After curing with ultraviolet light, the specific pattern was observed through the light-cured film visually and evaluated based on the following criteria: ◎: the specific pattern is clear; ○: the specific pattern is slightly blurred; △: the specific pattern is blurred; ╳: A specific pattern cannot be observed.

3. Adhesiveness

According to the ASTM D3359 test standard, the light-cured films of the composite films prepared in the above Examples 1 to 17 and Comparative Examples 1 to 9 were cut into 10 × 10 pieces (100 pieces) with a box knife or a small knife, and the size was 1 mm × Small squares of 1mm, then stick with 3M600 tape and hold one end of the tape with your hands, quickly tear off the tape in the vertical direction (90 °), observe the number of small squares stuck by the tape, and calculate the peeling area relative to the total area The area percentage is evaluated based on the following criteria: ○: 5B; △: 4B; ╳: 3B to 0B; of which, 5B is smooth and complete at the intersection of the incision without any peeling of the coating film; 4B, there is a small piece at the intersection of the incision Exfoliation, area percentage of peeling area ≦ 5%; 3B, exfoliation at cutting edge and intersection, area percentage of exfoliation area is greater than 5% and less than or equal to 15%; 2B, on cutting edge, intersection and small square With peeling, the area percentage of the peeling area is greater than 15% and less than or equal to 35%; 1B, there is peeling at the cutting edges, intersections and small squares, and the area percentage of the peeling area is greater than 35% and less than or equal to 65%; 0B , On cutting edges, intersections, and small squares Flaking, peeling area area percentage greater than 65%.

4.Antistatic

The surface impedance tester (manufactured by Static Solutions Inc., and its model number is RT-1000) was used to measure the impedance values of the composite films prepared in the foregoing Examples 1 to 17 and Comparative Examples 1 to 9, and performed on the basis of the following Evaluation, where the voltage of the impedance tester is set to 110 volts: ◎: impedance value ≦ 10 ¹⁰ ; ○: 10 ¹⁰ <impedance value ≦ 10 ¹¹ ; △: 10 ¹¹ <impedance value ≦ 10 ¹² ; ╳: 10 ¹² <impedance value .

5. Anti-fog

The composite films prepared in the foregoing Examples 1 to 17 and Comparative Examples 1 to 9 were set on the beaker cup mouth filled with water at 80 ° C., the light-cured film faced the cup mouth, and the surface of the light-cured film was 5 cm from the water surface.

After standing for 1 minute, visually determine whether fog has condensed on the surface of the light-cured film, and evaluate it according to the following criteria: ◎: There is no fog condensation, and evaporated water molecules adhere to the light-cured film and form a Flat water film (ie continuous water film); ○: There is no fog condensation, and evaporated water molecules adhere to the light-cured film and condense into an uneven water film; △: Some slight mist condensation; ╳: Fog condensation.

6. Contact angle

The contact angle of the light-cured film prepared by the present invention to water is measured by conventional technical methods and instruments, so it will not be repeated here.

7. Environmental test

The environmental test is to place the composite films prepared in the foregoing Examples 1 to 17 and Comparative Examples 1 to 9 in a high-temperature and high-humidity environment (an environment with a temperature of 65 ° C and a humidity of 80%). The composite film was taken out, and the aforementioned evaluation items were sequentially performed. Among them, the evaluation method of the change in impedance value after the environmental test is calculated according to the following formula (III), and evaluated according to the following criteria:

○: 0 <impedance value change <50; △: 50 ≦ impedance value change.

With reference to the results in Tables 1 and 2, it can be known that the cationic surfactant of the present invention and the photocurable film prepared by the photocurable resin material have good surface properties, and after environmental tests, the cationic interface activity of the present invention The agent also does not cause the defects of conventional sticking.

Secondly, the light-cured film prepared by the present invention also has good appearance properties and adhesion, and can be attached to various substrates without affecting its visual evaluation. Among them, the composite film prepared by the present invention has good antistatic property and anti-fogging property, and can further restrain the damage of the conventional static electricity and / or moisture to the device or the substrate. In Table 2, according to the evaluation results of Comparative Examples 1 to 9, it can be known that when the photocurable resin composition does not include the cationic surfactant of the present invention, the prepared photocurable film has poor antistatic properties and / or The anti-fog property, or the appearance or adhesiveness of the light-cured film cannot meet the application requirements.

In addition, after the light-cured film prepared by the present invention is subjected to environmental tests, its surface properties, antistatic properties, and anti-fog properties are not reduced. Accordingly, the cationic surfactant of the present invention has good stability.

It can be known from the examples and comparative examples of the present invention that the cationic surfactant prepared by the present invention can effectively improve the antistatic property and antifogging property of the composite film prepared. Among them, since the double bond group of the cationic surfactant and the photocurable resin material can further generate a bond, the cationic surfactant prepared by the present invention can also effectively overcome the migration of conventional cationic surfactants. Defects, which in turn improves their stability over time.

Although the present invention has been disclosed as above in the embodiments, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field to which the present invention pertains can make various changes and modifications without departing from the spirit and scope of the present invention. Retouching, so the scope of protection of the present invention shall be determined by the scope of the attached patent application.

Claims (10)

A cationic surfactant has a structure represented by the following formula (I): In formula (I), R ₁ represents an alkyl group having 1 to 30 carbon atoms, an olefin group having 2 to 30 carbon atoms or a cycloalkane group having 3 to 30 carbon atoms; R ₂ represents 1 to 4 carbon atoms Alkyl, alkylalcohol, alkanoyl or alkylphenyl; R ₃ represents alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, and alkynyl having 2 to 5 carbons , Aromatic group, alkyl aromatic group, alkenyl aromatic group, or -OR ₄ ; R ₄ represents an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, aromatic group, alkyl aromatic group, and alkenyl group Aryl or ; R ₅ represents an alkenyl group having 2 to 5 carbon atoms; at least one of R ₁ , R ₂ and R ₃ has an unsaturated group; Y ₁ and Y ₂ each independently represent an alkylene group having 2 to 4 carbon atoms A ^- is an anionic hydrophilic group; n and m each independently represent an integer of 0 to 30, and the sum of n and m is 5 to 30. The scope of the patent application to item 1 of the cationic surfactant of, wherein the anionic hydrophilic group comprising ^{F -, Cl -, Br -} , I -, (SO 2 CF 3) 2 N - or And R ₆ represents methyl or ethyl. A method for manufacturing a cationic surfactant includes: performing a pre-reaction on a mixture to form an intermediate product, wherein the pre-reaction includes a first reaction, and the mixture includes the following formula (I-1) Amine compounds and epoxy compounds represented by the following formula (I-2): R ₁ -NH ₂ (I-1) In the formula (I-1), R ₁ represents an alkyl group having 1 to 30 carbon atoms, Alkenyl groups with 2 to 30 carbon atoms or cycloalkane groups with 3 to 30 carbon atoms; In formula (I-2), R ₃ represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, an aromatic group, an alkyl aromatic group, Alkenyl aryl or -OR ₄ ; R ₄ represents alkenyl having 2 to 5 carbon atoms, alkynyl having 2 to 5 carbon atoms, aromatic group, alkyl aromatic group, alkenyl aromatic group, or And R ₅ represents an alkenyl group having a carbon number of 2 to 5; and performing a quaternization reaction on the intermediate product and the compound represented by the following formula (I-3) to obtain the cationic surfactant, wherein The cationic surfactant has a structure as described in item 1 or 2 of the scope of the patent application, and n and m represent 0: R ₂ -A (I-3) In the formula (I-3), R ₂ represents carbon An alkyl group, an alkyl alcohol group, an alkyl fluorenyl group, or an alkylphenyl group having a number of 1 to 4; and A is a hydrophilic group. According to the method for manufacturing a cationic surfactant as described in item 3 of the patent application scope, after the first reaction is performed, the pre-reaction further includes: a product of the first reaction and a ring having 2 to 4 carbon atoms. The oxyalkyl compound undergoes a second reaction. The method for manufacturing a cationic surfactant as described in item 4 of the scope of patent application, wherein the cationic surfactant produced by the manufacturing method has the structure as described in item 1 or 2 of the scope of patent application, n and m Represents integers from 0 to 100, and the sum of n and m is greater than 0. The method for manufacturing a cationic surfactant as described in any one of claims 3 to 5, wherein the hydrophilic group contains a halogen atom, (SO ₂ CF ₃ ) ₂ N- or , R ₆ represents methyl or ethyl, and "*" represents a bonding position. A photocurable resin composition, comprising: a photocurable resin material; and the cationic surfactant as described in item 1 or 2 of the scope of patent application, wherein the use amount based on the photocurable resin material is 100 parts by weight The use amount of the cationic surfactant is 0.5 parts by weight to 30 parts by weight. A composite film includes: a substrate; and a light-curing film provided on one surface of the substrate, and the light-curing film is made of a light-curing resin composition as described in item 7 of the patent application scope. Formed by a photo-curing process, wherein the contact angle of one of the photo-curing film with water does not exceed 50 degrees. The composite film according to item 8 of the scope of the patent application, wherein a first impedance value of the composite film per unit area is less than 10 ¹¹ ohms. The composite film according to item 9 of the scope of the patent application, wherein after the composite film is placed in a high temperature and high humidity environment, a second impedance value of the composite film per unit area is less than 10 ¹¹ ohms, and the second impedance value A ratio to one of the first impedance values is less than 50 and greater than zero.