TWI242018B - Inorganically modified antibacterial PU material - Google Patents

Abstract

An inorganically modified antibacterial PU material uses a reactive quaternary ammonium salt antibacterial agent to be added during a PU reaction process for reaction with the PU. Next, the reaction mixture is reacted with a -NH2- containing silane to be bonded as a part of the PU structure. Thus, the antibacterial PU material can be applied on the surface of an inorganic material, such as metal, glass, etc., and can be used as a treatment agent for a long-lasting antibacterial PU material. Furthermore, the quaternary ammonium salt can form a covalent bonding effect with the surface of a material, and can be uniformly distributed on the surface of a material for achieving mechanical antibacterial effects without being released by dissociation, thereby achieving the effects of long lasting, safe, and eco-friendly. A chemical formula of the compound used in the invention, which is most capable of displaying the properties of the invention, has the following structure: (formula), in which the NH2 group on the silane can be substituted by Cl, mercaptide (SH), -CH2=CH2-, methacrylic acid, epoxypropane, etc.; R3 is selected from the follow group; R4 is an arbitrary group; F is a silicon-functional group, such as -OCH3, -OC2H5, -OC2H4OCH3, etc.

Description

1242018 V. Description of the invention (1) [Technical Field] The present invention relates to an inorganic modified antibacterial PU material, especially an antibacterial agent that has become a part of the PU structure due to the antibacterial agent, and can be used on the surface of inorganic materials such as metals and glass. Moreover, the antibacterial agent will not be lost and the antibacterial effect will not decrease with time. [Previous technology] The next day, your early field microbes (Mi cro-organi sm / —...) are divided into spherical (Coccus), rod (Bacillus), and linear (Trichobacteria) ), Spiral

(Spirillum) and so on. Microorganisms also include various pathogens, larger protozoa (protozoa) other than bacteria, smaller and smaller than bacteria (〇.〇2 #) # virus (Virus)-that is, intracellular bacteria jhtercellular-bacterium). Microorganisms are also related to the body, digestion, metabolizers, wine, soy sauce, vinegar and other foods that are indispensable =, alcohol, butanol, propane, lactic acid, citric acid, anti-biomass, etc. Those who lack it have eight important functions in preventing public hazards. However, 200,000 or more microorganisms are still used as harmful helmets for human beings. Xi Xi · Liang Zhupei, a fruit-like medicine, Hungarian% = I There are many people in the country, and there is no universal effect.

Sex: ίΐ: 2 acid resistance, the danger of drugs, toxicity to the human body: cancerous, and the impact on genetic factors are all problems. Health, hygiene and well-being make the quality of the products more and more demanding. Also, with a few months of work ... b has become a necessity of life. Traveling around high-density residential buildings. Increased chances of imported infections caused by an increase in the number of mouths. Seventy-two years later, the ageing society is coming, and the people are clean on the environment.

1242018 V. Description of the invention (2) 2 Safety awareness will definitely increase, and the demand for products with antibacterial functions will be more and more. Antibacterial material-derived products refer to products with added antibacterial materials. These Kinki applications are concentrated in the early 20th century. Since the beginning of τ 2 in daily necessities and home appliances, it has rapidly expanded to construction and interior decoration materials, plastic rubber, coatings, food packaging materials and fiber clothing: even high-tech and high value-added products The requirements of the equipment, such as traditional equipment, are also shown in turn. ~, Metal materials such as stainless steel for human body connection / complex use (the proportion of people's livelihood uses accounts for 80%), bathroom accessories such as handrails, door handles, faucets, knife tableware, decorative second-hand conditioner and stainless steel medical appliances Etc.), and glass anti-corrosion ::: 2nd door on the 5th floor ®) 'If antibacterial treatment can be performed, antibacterial I can be expanded. Only worship the surroundings to enhance the integrity of antibacterial. The purpose of adding antibacterial material to the product is to make the surface resistance of the material in time by contacting the surface of the material to prevent the multiplication of microorganisms. The purpose of hygiene and safety is to reduce cross-infection and the spread of disease. Knowledge of materials 'long-term, safe, pollution-free sterilization and disinfection of new materials Qiu Er Er; what is the problem of brothers' health protection, which is the focus of the world's disinfection and public Er ίϋί and the focus of material developer research, so far JJ :: Species: t means that the development of new materials for sterilization and disinfection can directly investigate and see the killing of bacteria. It will be-to be studied: there are commonly used antibacterial technology. The key points are as follows: including antibiotics i〇tiCS) Fourth, and (quarter) _ Wquarternary ammonium

1242018

compounds), inorganic antibacterial agents [such as silver (siive) r saits, copper and zinc salts], iodine, and others. The use of these antibacterial agents is from slow release to Dissolving in the surroundings / in the night 'and then killing the bacteria present in the solution. As for the mechanism of action of antibacterial agents and antibacterial materials, human level 1 is divided into the following two categories: (a) First, it is necessary to enter the cells of bacteria, and after it acts, it cannot continue to replicate its genetic material and produce antibacterial effects ... The mechanism of action, if silver salts are used (the effect is better than copper salts, but the price is more expensive) as an example, when the bacteria are in contact with them, the slow-release inorganic silver salts can penetrate the bacterial cell membrane and enter the cytoplasm. Then, the hydrogen is replaced with the sulfur-hydrogen bond on the bacteria's ribonucleic acid or DNA to form a silver sulfide bond, so that the bacteria cannot continue to replicate their genetic material and produce an antibacterial effect. The action mechanism of other organic series of small molecule antibacterial agents, #because it penetrates into the cytoplasm of bacteria ', and then inhibits the relevant metabolic mechanism in the bacterial cell, making the bacteria unable to complete the replication action and produce antibacterial effects. It can also be used. However, such slow-release type antibacterial agents will not be able to become long-acting products after they have been released, and they can cause related pollution when they are released into the environment. The positive function of the money salt functional group can make the surface layer of the bacteria or damage its cell membrane, resulting in death due to the inability to follow the normal preparation or loss of protection of the fungus. The active part of the φ quaternary ammonium salt series antibacterial agent is Quaternary ammonium functional group, which can

Page 10 1242018

The quaternary salt functional group is positively charged, and can cause negative electricity induced in the surface of bacteria in contact with it. Bacteria can be caused by uneven surface nuclear distribution.异常 The cytoplasmic metabolism is abnormal, which makes it unable to continue to replicate the genetic material and produce antibacterial effect. Membrane 1 says' because the quaternary ammonium salt series of antibacterial agents interact with the similarity of the molecular structure of the scale S | (phospholipids) used to make up the cell, causing Γ to destroy the cell membrane of the bacteria and expose the cytoplasm inside it. Bacteria can not survive and lead to death due to lack of the protective effect of cell membrane, so as to achieve the purpose of antibacterial and sterilization.

Compared with the above-mentioned (a) dissolution-type slow-release antibacterial agent, this material is regarded as mechanical sterilization, so it does not need to penetrate the cell membrane to enter the cell # ί cytoplasmic effect, thereby inhibiting the intracellular correlation of bacteria Metabolic mechanism, the two bacteria can not complete the replication action to achieve antibacterial effect, so it is not easy to cause mutations in the field bacteria to produce drug resistance. However, it is generally known that the reduction of antibacterial products will eventually lose the antibacterial effect. The bactericide is an additive type and does not participate in causing the loss of the antibacterial agent, which eventually becomes [content] 爰 Yes, the main purpose of the present invention is to avoid the existence of the lack of the present invention. Long-term effective, safe, non-office series of antibacterial agents are formed on the surface of the material when they are distributed on the surface of the material. The antibacterial effect will gradually increase with time. This is because of the resistance of the antibacterial product. Bonded to substrate without antibacterial effect. The purpose is to solve the above-mentioned shortcomings. The quaternary ammonium salt series of antibacterial agents are designed to be a new sterilization and disinfection material. When the quaternary ammonium salt is covalently bonded, and the uniformity can be controlled.

«11 pages of 1242018 results. The purpose mentioned above should be added to the reaction. Part of the inorganic material added to reduce the surface of the covalent bond is mechanically efficient. V. Description of the invention (5) Pollution-free effect is to reach the agent, in PU Anti-burning (silane becomes a PU structure and will increase with time, etc., and the surface of inorganic antibacterial PU surface will form a surface, and it can achieve long-term effect by adopting the method. [Implementation method_ related examples—: The method of the present invention is to use diol (Polyol into tin The catalyst and reaction formula are as follows: Use reaction type 4 and then form part of the belt structure. It will be lost and the resistance is' can be used as a material treatment agent. Grade (quaternary) ammonium salt controls the effect of uniform free release. Grade ammonium salt antibacterial Because of the antibacterial effect of -N H2, Shi Xi is not metal and glass and is a long-term material. It is a kind of long isocyanate. (1 mo 1) '本 发Participate in PU bond formation to improve the anti-bacterial agent with antibacterial and antibacterial function. The effect is sterilizing, safe and effective. It is not effective for PU binding agent, such as bacteria PU material, and it will not harm the invention. Details and Technical description, it is explained that if the composition of the after-effect inorganic modified antibacterial PU material, the composition (di isocyanate) (2mol) is reacted with the polymulticomponent, at 70 ~ 8 5 ° C, react for 1 ~ 2hr and add> cereal A prepolymer (pre ρ ο 1 ymer) is formed, HO-R2—train-^ cnsRi_hc〇 +

〇CH-Rd -Rr

-NCO -o -R.2 one 10 '

Page 12 1242018 V. Description of the invention (6)

OCN ^-^ NCO ′ reuse prepolymer (2mON) reacts with a το alcohol (chain extender) (lm〇1) containing a four-level ammonia, the reaction formula is as follows

-¾——OH Ο Ο OCN '^^ f'l—C —〇 —Rj—〇—C—N * λλ-N0 Η Η 〇 Then it is combined with Silane (SlUne) with -question 2 (Chemical 〇1 ) Reactions ~ U-agents produced by inorganic modified antibacterial pu materials on the surface of inorganic materials such as metals and glass, and a treatment agent with long-acting antibacterial PU materials. Reaction formula 2 = · Λ rh Τ7

OCN oJ.

O

F +

II 3—0—c—n ^ nc u o • Si— F I F

—Si— F Among them, the amine group (NH2) on the silane (si lane) (f) can be gas ion (Cl), thiolate (jjjercap ^ de; SH), ethylene H3C., And propylene oxide (-CH2 = CH2-), methacrylic acid (h2C '\

Page 13 1242018

Page 14 1242018 V. One of the descriptions of the invention (8): hydrogen, alkyl, alkenyl, alkynyl, acyl, aryl, carboxyl (carboxylate), alkoxycarbonyl, aryloxycarbonyl, car boxam i do, alky lamino, acy 1 am i no, alkoxy (A 1 koxy 1), acyloxy, hydroxyalky 1, alkoxyalkyl, aminoalkyl, alkylamino, thio, thio 1 ky 11 hio), thioalkyl, alky ithio, carbamoyl, urea, thiourea, su 1 f ony 1, sulfonic acid ( sulfonate), su 1 f onam i de, sul f ony lamino, and sui fonyioxy. X is one of the following halogen elements: fluorine (F), chlorine (C1), bromine (Br), iodine (I), and stone (At). The η system is from 1 to 1 0 0 0. The y system is 1 to 10, and the priority is 1 to 3. In addition, the group O11 in the structural group of the above & may be substituted by an amine group (M1). R4 is an arbitrary group; F is a silicon functional group (silicon_functiochal-och3, -〇c2h5, -〇c2MCH3, etc.) g) as in Example 2: Another composition of the present invention is based on two different Cyanate (diiS0cyanate) (2m〇1) and polyhydric alcohol (= iy〇i) (im〇i) reaction, at 70 ~ 85 ° C, reaction for 2hr and add tin catalyst and solvent together

1242018

Then it reacts with siiane (2m〇i) with -NH2 to form an inorganic modified antibacterial pu material treatment agent that can be used on the surface of inorganic materials such as metals and glass, and is a long-acting antibacterial PU material. Treatment agent, the reaction formula is as follows:

OCN 〇 C—〇—R3 + Ο

F H2NE4—Si— F F

—O—R3

II 1242018 V. Description of the invention (10) F H2NR4—Si—F Among which, the amine group (NH2) on silane (f) may be chloride (C1), mercaptide (SH), acetamidine 〇— Η3α-CH2 = CH2-), methacrylic acid (η〆o 'H2C —CH——), etc.

C% 〇 and propylene oxide

HO -R- -E-OH _

R

R

0 nX and

Page 17 1242018

V. Description of Invention (11) P

In addition, in the structural group of R3, R is one of the following elements or groups: hydrogen, alkyl, aikenyl, alkynyl, and acyl , Aryl, carboxy late, alkoxycarbony 1, aryloxycarbonyl, carboxamido, alky lamino, acy lamino , Alkoxy 1, acyloxy, hydroxyalkyl, alkoxyalky 1, aminoal kyl, alky lamino, thio group, thi ο, Thio (a 1 ky 11 hio), thioalkyl, alkylthio, carbamoyl, urea, thiourea, sulfonyl, sulphonic acid ( sulfonate), sulfonamide (su 1 fonam i de), sul fony lamino and sui fonyioxy. X series is one of the following halogen elements: fluorine (F), chlorine (C1), bromine (Br), iodine (I), and stone diuretic (At). The η system is from 1 to 1 0 0 0; the y system is from 1 to 1 0, preferably between 1 and 3. In addition, the OH group in the structural group of R3 may be replaced by an amine group (NH2).

Page 18 1242018 V. Description of the invention (12) R4 is an arbitrary group; F is silicon-functional group (0CH3, -〇c2H5, -〇C2H4OCH3, etc.) If so, the antibacterial PU material of the present invention It is based on the addition of silane surface treatment agent that participates in the PU reaction and bond 2 so that the resist will not be lost and has an antibacterial effect. In addition to the anti-Qi of the present invention, such as most antibacterial and antibacterial agents, this The mechanism is always strong; and the fourth level of the present invention has a key connection effect, and can control mechanical sterilization, and does not swim efficiently, safely, and harmlessly, but the above is only the scope of the present invention. Such changes and modifications are all For example, antibacterial PU material is a reactive quaternary ammonium salt antibacterial agent with long-lasting antibacterial effect. It forms a part of the PU structure in the p U reaction, and then reacts with) # to attach to metal and glass. Inorganic bacterial agents have become part of the structure of PU, so the antibacterial effect will not decrease with time. The mechanism of antibacterial function is different. Currently, the role of the commercially available inorganic series of antibacterial agents is to dissolve or slow release the f-wash bar. then It will slowly lose and lose antibacterial ... Gansu forms a covalent ionization with the surface of the material ^ The preferred embodiment of the contacting machine can achieve the long-acting type of Changming. It is not intended to limit the application of the special application according to the present invention. The scope of Rikui M's monthly insults is covered by the Maoming patent.

1242018 Simple illustration of the drawing None ΙϋϋΙ 第 20

Claims (1)

County pick} Original (revised) original VI. Patent application scope 1. An inorganic modified antibacterial PU material, which contains the following formula (I): 〇〇 + II II OCN ΛΛ / + Ι —C —0 ——0 —C —Ni / vn-NC H 3 HO F —Si— FF F H2NE4—Si—F i F Among them, the amine group (NH2_ on silane) (f) can be chloride ion (Cl), mercaptide (SH), ethylene H3C. Ο— -C \ And propylene oxide (-CH2 = CH2-), methopropanoic acid (h2c oo (H2C-CH-), etc.) R3 is selected from the group consisting of: -0H HO -R- R φ -R- R OH χθ Page 21 1242018 6. Scope of patent application HO -R HOR ROH 2X R- OH 0 nX and R4 is an arbitrary group; F is a silicon-functional group, such as -0CH3, -0C2H5, -0C2H40CH3, and the like. 2. The inorganic modified antibacterial PU material as described in item 1 of the scope of the patent application, wherein the 〇IIII OCN ^ tl —C —0 —R3 〇1C —N NC Η 3 HO Polymer (prepolymer OCH ——Rj—Η-C——〇 ——R.2—O '-Η ——R ± —NCO OCN ^^ NCO Reuse prepolymer (prepolymer) with a quaternary ammonia salt Dihydric alcohol 1242018 VI. Composition of patent extension (chain extender) reaction composition; Also, & is a diisocyanate with different structure; R2 is a polypolyol with different structure. The inorganic modified antibacterial PU material of formula (I) according to the item, wherein R in the structural group of R3 is one of the following elements or groups: hydrogen, alkyl, alkenyl (Alkenyl), alkynyl, acyl, aryl, carboxylate, alkoxycarbonyl, ary loxycarbony 1, car boxam i do , Alky lamino, acy lamino, alkoxy (a 1 koxy 1), acy loxy, hydroxyalkyl hydroxyalky 1), alkoxyalky 1, amine alkyl (am i noa 1 ky 1, a 1 ky 1 am i no), thio, thio, a 1 ky 11 hio , Thioalkyl, alky lthio, carbamoyl, urea, thiourea, su 1 f ony 1, sulfonate, amine (Su 1 f onam i de), thiamine (3111 £ 〇1 ^ 131111110), and thionine (3111 {〇1171〇 and 7). 4. Formula (i ) Of the inorganic modified antibacterial PU material 'wherein X in the structural group of r3 is one of the following halogen elements: fluorine (F), chlorine (C1), bromine (Br), moth (I), Shi'er (At 5. The inorganic modified antibacterial PU material of formula (I) as described in item} of the patent application scope, wherein the structural formula group of the heart is 1 to 1000. 6. As applied Inorganic modification antibacterial of formula (I) described in item} Page 23 1242018 VI. Scope of patent application u Materials, among which the structural group of the heart is selected between 1 and 3. y is 1 to 10, and the PU material as described in item 丨 of the patent application scope is preferred, wherein the inorganic modification resistance (called R = C) is replaced. -The group in the structural group may be amino-based bacteria, an inorganic modified antibacterial PU material, which contains the following formula: ⑴ 0 〇CN-w | j—C— 〇 F H2NR ^ —Si-F + FO II FI HjNR ^ —Si— F where the amine group (NH2) on the silane (Si lane) (F) can be chloride (Cl), mercaptide (SH), ethylene h3c. O-(-CH2 = CH2- ), Mevalonate (h2cT -α ο and propylene oxide ο H2C-CH-etc.) are selected from the group consisting of: Page 24 1242018 6. Scope of patent application -OH HO -R- HO R 0 OH χΘ -R-OH -R- R ηχ and RR—N ~ R (CH2) y HOR- -ROH R- (CH2) y 2X R is an arbitrary group; F is a silicon-functional group, such as -0CH3, -0C2H5, -0C2H40CH3, etc. 9. The inorganic modified antibacterial PU material of formula (I I) as described in item 8 of the scope of patent application, wherein the Page 25, 1242018 VI. Scope of patent application y 〇 0 -J · η II II Γ —Sl-R4 ^ | j ^ C -Jj -tj —c —r3 F is composed of a prepolymer (prep〇lymer 0 OCN ~ Rl—η-C-0-R.2—0—c · -Ri—NCO (OCH njn ^ NCO) 'Reuse prepolymer and a single -OH quaternary ammonia salt / HO- ~ H3 (chain extender) reaction composition; In addition, the heart is a diisocyanate of different structure; R2 is a polypolyol of different structure. 10. Formula (II) as described in item 8 of the scope of patent application The inorganic modified antibacterial PU material, wherein R in the structural group of R3 is one of the following elements or groups: hydrogen, alkyl, alkenyl, alkynyl ), Acyl, aryl, carboxylate, alkoxycarbonyl, ary 1 oxycarbony 1, carboxamido, carbamide (a 1 ky 1 am i no), acy 1 am i no, a 1 koxy 1, acyloxy, hydroxyalkyl, a 1 koxy a 1 ky 1 ), Amines (am i noa 1 ky 1, a 1 ky 1 am i no), thio, thio, alkylthio, thioxanyl 1242018 6. Scope of patent application (thioalkyl, alkylthio), carbamoyl, urea, ureurea, thiourea, su 1 f ony 1, sulfonate, stone yellow Amine (su 1 f onami de), sulfonylamino (sulfonylamino) and sulfonyloxy (sulfonyloxy) 〇1 1. The inorganic modified antibacterial PU material of formula (II) as described in item 8 of the scope of patent application, wherein In the structural group of R3, X is one of the following halogen elements: fluorine (F), chlorine (C1), bromine (Br), iodine (I), and stone (At). 1 2. The inorganic modified antibacterial P ϋ material of formula (11) as described in item 8 of the scope of patent application, wherein η in the structural formula group of r3 is 1 to 100; 1 3, such as The inorganic modified rubidium-resistant PU material of formula (II) described in item 8 of the scope of the application for patent, wherein 'y' in the structural formula group of R3 is 1 to 10, and preferably 1 to 3 is selected. 14. The inorganic modified antibacterial PU material of the formula (I I) as described in item 8 of the scope of the patent application, wherein the 0H group in the structural group of the above-mentioned heart may be substituted by an amine group (N H2). Page 27