WO2017107423A1

WO2017107423A1 - Freeze-resistant acrylate pressure-sensitive adhesive, method of preparing same, and application thereof in preparation of freeze-resistant acrylate pressure-sensitive label

Info

Publication number: WO2017107423A1
Application number: PCT/CN2016/087982
Authority: WO
Inventors: 李书锋; 李书芒; 周秋妹
Original assignee: 广州市金万正印刷材料有限公司
Priority date: 2015-12-24
Filing date: 2016-06-30
Publication date: 2017-06-29
Also published as: CN105400464B; CN105400464A

Abstract

The present invention discloses a freeze-resistant acrylate pressure-sensitive adhesive, a method of preparing the same, and an application thereof in preparation of a freeze-resistant acrylate pressure-sensitive adhesive label. The freeze-resistant acrylate pressure-sensitive adhesive is formed by free radical polymerization of comonomers. The comonomers comprise the following in parts by weight: 20 parts to 50 parts of isooctyl acrylate, 150 parts to 200 parts of butyl acrylate, 50 parts to 100 parts of acrylic acid, 10 parts to 70 parts of 2-ethylhexyl acrylate, 100 parts to 200 parts of ethyl acetate, 300 parts to 450 parts of toluene, and 3 parts to 5 parts of benzoyl peroxide. In the present invention, an improved formula and a novel label manufacturing process are combined to address an adhesive overflow problem caused by a low molecular weight, insufficient cohesive energy, and flexibility of the adhesive. The freeze-resistant acrylate pressure-sensitive adhesive label of the present invention has superior flexibility and stable performance, and is used in labeling refrigerated blood bags and other refrigerated items without an undesirable phenomenon such as warping or peeling. Therefore, the present invention addresses an existing problem of the difficulty to automatically stick a blood bag label on the surface of a blood bag at -30°C.

Description

Frost-resistant acrylate pressure-sensitive adhesive, preparation method thereof and application thereof in preparing frost-resistant acrylate pressure sensitive label

Technical field

The invention relates to a medical pressure sensitive adhesive and a preparation method and application thereof, in particular to a freeze-resistant acrylate pressure sensitive adhesive, a preparation method thereof and the application thereof in preparing a freeze-resistant acrylate pressure sensitive label.

Background technique

With the development of medical technology, blood transfusion has become a more common treatment process. The earliest blood transfusions are delivered to patients immediately after blood collection from blood donors. There is no preservation problem. Now it is generally the blood in the stock, that is, the blood has a short shelf life in the blood bank. In order to input the most effective blood, that is to say, to preserve the viability of the cells, so that they can continue to survive after input, they can perform their intended functions. Therefore, it is necessary to try to solve various kinds of cell damage that may be caused during storage. Problems such as blood containers, anticoagulants, preservation solutions, etc. The usual standard for measuring blood eligibility is to look at the blood input for 24 hours, after which the survival of the red blood cells can reach 70% of the input, if it can reach 70%, it is qualified.

In order to ensure the safety of blood transfusion, the loss of "whole blood" has been replaced by the "component blood", various blood components can be harvested from a single donation of whole blood, the general blood bank can separate red blood cells and plasma components, and some can be prepared Ingredients such as: platelet concentrates and cryoprecipitates. Whole blood and component blood are usually stored in blood bags.

Usually, the blood of a blood donor is collected in a blood transfusion center, in a blood bank of a hospital, at a mobile blood collection center, and then the blood is sent to a laboratory for testing and processing into components for storage, and then distributed when necessary. The blood collected at body temperature, i.e., 37 ° C, must be cooled to below 10 ° C for transport to maintain its important properties, and stored in an environment of about 4 ° C until use. If blood cannot be stored or transported at these temperatures, it loses the ability to deliver oxygen or carbon dioxide to tissues and free tissue, respectively, during transfusion. If the blood is exposed to a warm environment, it poses a risk of bacterial contamination.

Specifically, whole blood and red blood cells must be stored between +2 ° C and +6 ° C. If whole blood and red blood cells are not stored between +2 ° C and +6 ° C, its oxygen carrying capacity will be greatly reduced. At the same time, whole blood and red blood cells can be stored between +2 ° C and +6 ° C in the blood device. The growth of any bacterial contamination is kept to a minimum. If whole blood and red blood cells are stored above +6 ° C, bacteria that inadvertently enter the device during the collection process can grow to a degree where the blood transfusion of contaminated blood can be fatal. Red blood cells are very sensitive to freezing. If it is stored below +2 °C, the blood is frozen, red blood cells are broken and hemoglobin is released; that is, red blood cells are hemolyzed, and hemolyzed blood transfusion is also fatal.

Fresh frozen plasma (FFP) is plasma isolated from whole blood within a 6 to 8 hour collection and is rapidly frozen and stored at -20 ° C or lower. The optimum storage temperature is -30 ° C or lower, there is no lower limit of FFP storage temperature.

Plasma contains water, electrolytes, clotting factors and other proteins (mainly albumin), most of which are stable at refrigerator temperatures, ie +2 ° C to +6 ° C. However, if it is not stored at a temperature of -20 ° C or lower, factor V and factor VIII, which are essential in the coagulation mechanism, will deteriorate or decrease in number, and greatly reduce plasma clotting activity. FFP can be administered to a patient to restore or help maintain a coagulation factor such as Factor V or Factor VIII. Cold precipitation is the cold insoluble portion of the plasma remaining after the FFP has thawed before +1 °C and +6 °C, and can be used to correct certain coagulation defects. It contains about 50% Factor VIII and von Willebrand factor, 20%-40% fibrinogen and some factor XIII originally present in fresh plasma.

Plasma was isolated from red blood cells collected in the blood for 6-8 hours, and the plasma was a solidified solid within 30 minutes of rapid, defined separation from the cells. The plasma is then slowly thawed below +4 °C. In order to obtain the highest yield of Factor VIII from cryoprecipitation of plasma devices, it is important to strictly adhere to standard procedures for collection, storage and ingredient processing. The stability of storage depends on the available storage temperature. The optimum storage temperature is below -30 °C. Therefore, whole blood and red blood cells must be stored at +2 ° C to +6 ° C and transported between +2 and +10 ° C. The optimal storage temperature for fresh frozen plasma and cryoprecipitate is -30 ° C and below.

In the blood supply industry, according to the requirements of “one law and two regulations”, in order to ensure the safety of blood transfusion, products prepared by the blood center and the central blood station, and qualified products are required to be registered and checked before the blood transfusion of the patient in the hospital. This requires the blood bag to be labeled in the case of freezing. Currently, there is no label on the market that can be automatically labeled on a blood bag of -30 ° C. The current practice is to manually label or pass the layered labeling. The method is to paste the label into the frozen blood bag after repeated pressing, which affects the health of the labeling worker and affects the labeling efficiency.

Chinese patent application number: CN103843051 A discloses a labeling method by adding a layer label which can be easily removed after the labeling blood bag is removed from the refrigerator. That is, a layer or a plurality of labels are pre-applied to the blood bag at normal temperature, and then refrigerated, and the blood bag is taken out from the refrigerator during use, usually the blood bag contains the frozen surface of the blood bag label or a layer of frost or ice. Crystal (depending on the temperature of the bag). After the outer layer is removed, the fresh receiving surface of the original label is exposed and a supplemental label is applied thereto. However, this method can only be artificially labeled, which is easy to produce errors, and the labeling efficiency is low; the technology can not meet the labeling requirements of blood stations and hospitals, and can not meet the requirements of continuous labeling of automatic labeling machines. In particular, it is not possible to attach the original label to the blood bag at -30 °C.

Summary of the invention

In order to overcome the defects of the prior art, the object of the present invention is to provide a freeze-resistant acrylate pressure-sensitive adhesive for preparing a frost-resistant pressure-sensitive adhesive label, improving the labeling efficiency, and preventing the label from falling off in a frozen environment.

In order to achieve the above object, the technical solution adopted by the present invention is as follows:

A freeze-resistant acrylate pressure sensitive adhesive formed by free radical polymerization of a comonomer, the comonomer comprising

20-50 parts by weight of isooctyl acrylate,

Butyl acrylate 150-200 parts by weight,

50-100 parts by weight of acrylic acid,

2-ethylhexyl acrylate 10-70 parts by weight

Ethyl acetate 100-200 parts by weight,

Toluene 300-450 parts by weight,

Benzoyl peroxide (BPO) is 3-5 parts by weight.

In a further aspect, the comonomer of the freeze-resistant acrylate pressure sensitive adhesive of the present invention comprises:

30-40 parts by weight of isooctyl acrylate,

Butyl acrylate 160-180 parts by weight,

60-80 parts by weight of acrylic acid,

2-ethylhexyl acrylate 20-70 parts by weight

Ethyl acetate 120-150 parts by weight,

Toluene 350-400 parts by weight;

Benzoyl peroxide (BPO) 4-5 parts by weight.

In a further embodiment, the comonomer of the present invention further comprises from 0 to 70 parts by weight of vinyl acetate.

In a further embodiment, the comonomer of the present invention further comprises 20-50 parts by weight of hydroxyethyl acrylate.

Another object of the present invention is to provide a method for preparing a freeze-resistant acrylate pressure-sensitive adhesive, which comprises the following steps:

1) Dissolving 1-2.6 parts by weight of benzoyl peroxide (BPO) in 40-60 parts by weight of ethyl acetate, and then adding a formula amount of isooctyl acrylate, butyl acrylate, acrylic acid, acrylic acid - 2 B Hexyl hexyl ester, toluene, stirred and mixed uniformly to obtain a mixed solution;

2) 30-50 parts by weight of ethyl acetate is added to the reactor to raise the temperature to 76-80 ° C, after the reflux is stabilized, slowly start adding 1/2 volume of the above mixture, and react at 80-82 ° C for 1-1.5 hours;

3) Dissolve the remaining benzoyl peroxide (BPO) in the remaining ethyl acetate while the reaction of step 2), and divide it into 10-30 parts by weight of three parts of ethyl benzoyl peroxide (BPO) in ethyl acetate solution. Add one of the components to the reaction system of step 2) and keep it for 1 hour; then slowly add the remaining 1/2 volume of the mixture to the reaction system at a reaction temperature of 80-82 ° C, and add the time. Control was carried out for 2-3 hours; after completion of the dropwise addition, a portion of ethyl acetate solution of benzoyl peroxide (BPO) was continuously added dropwise to the reaction system, and the reaction was kept for 1 hour, and the last portion of benzoyl peroxide was added dropwise again. The ethyl acetate solution of (BPO) was reacted at 80 ° C for 1.5 to 2.5 hours after the completion of the dropwise addition to obtain an acrylate pressure-sensitive adhesive which was subjected to freezing.

A third object of the present invention is to provide a freeze-resistant acrylate pressure-sensitive adhesive label produced by using the freeze-resistant acrylate pressure-sensitive adhesive of the present invention.

A fourth object of the present invention is to provide a method for preparing a freeze-resistant acrylate pressure-sensitive adhesive label, which comprises the following steps:

A) In the freeze-resistant acrylate pressure-sensitive adhesive of the present invention, the curing agent is added in a ratio of the mass ratio of the acrylate pressure-sensitive adhesive to the curing agent of 100: (0.1-0.5), dispersed and uniformly mixed, and then applied to the silicone oil. On the bottom paper, it is cured at 115-135 ° C to form a cured adhesive layer, and then the film substrate is pasted on the surface of the adhesive layer, and placed in a baking oven to be matured to obtain a first layer of acrylic pressure-sensitive adhesive layer;

B) taking the acrylate pressure sensitive adhesive of the present invention, coating it on a silicone oil base paper, and curing at 115-135 ° C to obtain a second layer of acrylate pressure sensitive adhesive layer;

C) removing the silicone oil base paper in the first layer of the acrylic pressure-sensitive adhesive layer described in the step A) to expose the cured adhesive layer, and then laminating the second layer of the acrylate pressure-sensitive adhesive layer of the step B) on the cured adhesive layer. A freeze-resistant pressure sensitive adhesive label is produced.

In a further aspect, the curing agent of the present invention is a mixture of an isocyanate and an epoxy resin, and the mass ratio of the two is 1:1.

In a further aspect, the silicone oil base paper of the present invention is one of glassine silicone oil base paper, PET silicone oil base paper, and PP silicone oil base paper; the film base material is one of PET, BOPP, PP, and PE. Kind.

In a further aspect, the cured adhesive layer of the present invention has a thickness of 30-35 μm; and the total thickness of the freeze-resistant pressure-sensitive adhesive label is 40-55 μm.

Compared with the prior art, the beneficial effects of the present invention are:

1. The invention combines a new label preparation process by improving the formulation of the acrylate pressure-sensitive adhesive, and at the same time solves the problem of “overflow” in order to solve the problem of low molecular weight, insufficient cohesive energy and soft gel;

2. The freeze-resistant acrylate pressure-sensitive adhesive label prepared by the freeze-resistant acrylate pressure-sensitive adhesive of the invention has soft label and stable performance, and is suitable for labeling blood bags and other refrigerated articles for refrigerating. The blood bag and its blood bag can not be lifted or opened, which can solve the problem that the existing blood bag label is difficult to be automatically labeled on the blood bag at -30 °C.

detailed description

The present invention will be further described in detail below in conjunction with specific embodiments.

The freeze-resistant acrylate pressure-sensitive adhesive of the present invention is obtained by radical polymerization of a comonomer, the comonomer comprising

20-50 parts by weight of isooctyl acrylate,

Butyl acrylate 150-200 parts by weight,

50-100 parts by weight of acrylic acid,

2-ethylhexyl acrylate 10-70 parts by weight

Ethyl acetate 100-200 parts by weight,

Toluene 300-450 parts by weight,

Benzoyl peroxide (BPO) is 3-5 parts by weight.

30-40 parts by weight of isooctyl acrylate,

Butyl acrylate 160-180 parts by weight,

60-80 parts by weight of acrylic acid,

2-ethylhexyl acrylate 20-70 parts by weight

Ethyl acetate 120-150 parts by weight,

Toluene 350-400 parts by weight;

Benzoyl peroxide (BPO) 4-5 parts by weight.

3) Dissolve the remaining benzoyl peroxide (BPO) in the remaining ethyl acetate while the reaction of step 2), and divide it into 10-30 parts by weight of three parts of ethyl benzoyl peroxide (BPO) in ethyl acetate solution. Add one of the components to the reaction system of step 2) and keep it for 1 hour; then slowly add the remaining 1/2 volume of the mixture to the reaction system at a reaction temperature of 80-82 ° C, and add the time. Control was carried out for 2-3 hours; after completion of the dropwise addition, a portion of ethyl acetate solution of benzoyl peroxide (BPO) was continuously added dropwise to the reaction system, and the reaction was kept for 1 hour, and the last portion of benzoyl peroxide was again added dropwise. The ethyl acetate solution of BPO) is reacted at 80 ° C for 1.5 to 2.5 hours after the completion of the dropwise addition to obtain an acrylate pressure-sensitive adhesive which is subjected to freezing.

A) In the freeze-resistant acrylate pressure-sensitive adhesive of the present invention, the curing agent is added in a ratio of the mass ratio of the acrylate pressure-sensitive adhesive to the curing agent of 100: (0.1-0.5), dispersed and uniformly mixed, and then coated. On the silicone oil base paper, curing at 115-135 ° C to form a cured adhesive layer, and then attaching a film substrate on the surface of the adhesive layer, and placing it in a baking oven to obtain a first layer of acrylic pressure-sensitive adhesive layer; The first layer of acrylic pressure-sensitive adhesive layer prepared by the acrylate pressure-sensitive adhesive is cross-linked by the curing agent, the molecular weight is increased, the cohesive force is improved, and the problem of overflowing rubber is solved. Since the molecular weight of the adhesive layer crosslinked by the curing agent is increased and the cohesive force is increased, the problem of label labeling and lifting is solved;

B) taking the freeze-resistant acrylate pressure-sensitive adhesive of the present invention, coating it on a silicone oil base paper, and curing at 115-135 ° C to obtain a second layer of acrylate pressure-sensitive adhesive layer;

C) removing the silicone oil base paper in the first layer of the acrylic pressure-sensitive adhesive layer described in the step A) to expose the cured adhesive layer, and then laminating the second layer of the acrylate pressure-sensitive adhesive layer of the step B) on the cured adhesive layer. A freeze-resistant pressure sensitive label is produced; a first layer of acrylic pressure-sensitive adhesive layer is added with a second layer of acrylate pressure-sensitive adhesive layer, and the obtained frost-resistant acrylate pressure-sensitive adhesive label is pressure-sensitive by two layers of acrylate. The adhesive layer is overlapped, and the total thickness of the two adhesive layers is 40 μm-55 μm. Due to the two layers of glue elastomer, the surface glue is not crosslinked and maintains good adhesion, and two layers of acrylate are obtained. The pressure-sensitive adhesive layer overlaps the frost-resistant acrylate pressure-sensitive adhesive label, which achieves the purpose of automatic labeling in the environment of -30 ° C outer surface condensate or a layer of frost or ice crystal.

Preferably, in the above preparation method, the second layer of the acrylate pressure-sensitive adhesive layer is composited on the above-mentioned cured adhesive layer, and passes the Chinese patent number ZL2012 1 The lamination technique of the coating compounding process disclosed in 0431783.X is compounded.

Since the molecular weight size and distribution of the polymer have a large influence on the bonding characteristics (such as high temperature resistance and freeze resistance), when the molecular weight is small, it has a lower melting point, a smaller viscosity, and is adhered to the condensation property. Good performance, but low cohesive energy, insufficient cohesive strength, and easy to warp the small tube on the blood bag; difficult to dissolve when the polymer molecular weight is large, high melting point, high viscosity, for condensation In the environment, especially for frost or ice crystals that are subjected to the surface of the condensed blood bag, adhesion properties cannot be achieved. Since the freeze-resistant acrylate pressure-sensitive adhesive has good adhesion properties to withstand condensation characteristics, the molecular weight is low, the cohesive energy is insufficient, and the colloid is soft, and it is easy to overflow on the film substrate. Therefore, the present invention combines a new label preparation process by improving the formulation of the acrylate pressure-sensitive adhesive, and at the same time solves the problem of low molecular weight, insufficient cohesive energy, soft gel and "overfill". Therefore, the inventors have proposed a new strategy for the coating process.

In a further aspect, the cured adhesive layer of the present invention has a thickness of 30-35 μm; and the total thickness of the freeze-resistant pressure sensitive label is 40-55 μm.

The following are specific examples of the invention. In the following examples, the materials and equipment used can be obtained by purchase.

Example 1

A freeze-resistant acrylate pressure sensitive adhesive prepared by the following method:

1) First, 2.0 parts of benzoyl peroxide (BPO) was dissolved in 100 parts of ethyl acetate, and the mixture was thoroughly stirred to dissolve uniformly. After the dissolution was completed, 50 parts of the above-mentioned isooctyl acrylate and butyl acrylate were further added. 200 parts of ester, 30 parts of 2-ethylhexyl acrylate, 100 parts of acrylic acid, 10 parts of hydroxyethyl acrylate, 10 parts of vinyl acetate and 400 parts of toluene were stirred and mixed uniformly;

2) 40 parts of ethyl acetate was added to the reactor and the temperature was raised to 75 ° C. After the reflux was stabilized, 1/2 of the above mixture was slowly added dropwise, and the mixture was dropped in 1 hour; and the reaction temperature was controlled at 80-82 ° C; Add 20 parts of ethyl acetate dissolved in 0.5 part of benzoyl peroxide (BPO) dropwise, add dropwise in 10 minutes, and keep the reaction for 1 hour; then slowly add the remaining 1/2 monomer mixture. The dropping time is 2.5 hours, the reaction temperature is controlled at 80-82 ° C; then 20 parts of ethyl acetate dissolved in 0.5 part of benzoyl peroxide (BPO) is added dropwise, and the dropwise addition is completed in 10 minutes, and the reaction is kept for 1 hour; Further, 20 parts of ethyl acetate in which 0.5 part of benzoyl peroxide (BPO) was dissolved was added dropwise thereto, and the mixture was added dropwise over 10 minutes. After the completion of the dropwise addition, the mixture was reacted at 80 ° C for two hours to obtain a freeze-resistant acrylate pressure-sensitive adhesive.

Application Example 1

A freeze-resistant acrylate pressure sensitive adhesive label prepared by the following method:

1) 100 parts by weight of the pressure-sensitive adhesive prepared in Example 1, adding 0.1 part by weight of an epoxy resin and 0.15 parts of an isocyanate curing agent, dispersing at a high speed and uniformly transferring the paper to a subsurface synthetic paper through a glassy base paper. (PP synthetic paper), the dry glue thickness is 30 μm, and is cured at 115-135 ° C to obtain a first layer of acrylate pressure-sensitive adhesive layer, which is placed in a baking oven at 60 ° C for 72 hours;

2) taking 100 parts by weight of the pressure-sensitive adhesive prepared in Example 1, and uniformly dispersing at a high speed; peeling off the first layer of the acrylate pressure-sensitive adhesive layer, and then applying the adhesive to the glazing transfer coating. The first layer of the acrylate pressure-sensitive adhesive layer has a dry glue thickness of 15 μm and is cured at 115-135 ° C to obtain a frost-resistant acrylate pressure-sensitive adhesive label having two layers of glue overlapping.

The test results of the freeze-resistant acrylate pressure-sensitive adhesive label are as follows: the initial adhesion force is 15# steel ball; the blood-importing bag small tube has no uplifting, opening and the like, and the blood bag attached to -30 °C has no lifting phenomenon.

Example 2

1) First, 1.8 parts of benzoyl peroxide (BPO) was dissolved in 40 parts of ethyl acetate, and the mixture was thoroughly stirred to dissolve uniformly. After the dissolution was completed, 30 parts of the above-mentioned isooctyl acrylate and butyl acrylate were further added. 180 parts of ester, 50 parts of 2-ethylhexyl acrylate, 80 parts of acrylic acid, 50 parts of hydroxyethyl acrylate, 20 parts of vinyl acetate, and 450 parts of toluene are stirred and mixed uniformly;

2) 50 parts of ethyl acetate was added to the reactor to raise the temperature to 75 ° C, after the reflux was stabilized, the 1/2 of the above mixture was slowly added dropwise, and the dropwise addition was completed in 1.5 hours; and the reaction temperature was controlled at 80-82 ° C; Then add 20 parts of ethyl acetate dissolved in 0.4 parts of benzoyl peroxide (BPO), add dropwise in 20 minutes, and keep the reaction for 1 hour; then slowly add the remaining 1/2 monomer mixture. The dropping time is 2.0 hours, the reaction temperature is controlled at 80-82 ° C; then 20 parts of ethyl acetate dissolved in 0.4 parts of benzoyl peroxide (BPO) is added dropwise, and the dropwise addition is completed in 20 minutes, and the reaction is kept for 1 hour; Further, 20 parts of ethyl acetate in which 0.4 part of benzoyl peroxide (BPO) was dissolved was added dropwise thereto, and the mixture was added dropwise over 20 minutes. After the dropwise addition, the mixture was reacted at 80 ° C for 2.5 hours to obtain a freeze-resistant acrylate pressure-sensitive adhesive.

Application Example 2

1) Take 100 parts by weight of the pressure-sensitive adhesive prepared in Example 2, add 0.2 parts by weight of epoxy resin and 0.2 part of isocyanate curing agent, disperse at high speed, mix and transfer, and transfer to the sub-surface synthetic paper through glassine paper. (PP synthetic paper), dry glue thickness 35μm, solidified at 115-135 ° C, to obtain a first layer of acrylate pressure sensitive adhesive layer, placed in a 60 ° C oven for 72 hours;

2) taking 100 parts by weight of the pressure-sensitive adhesive prepared in Example 2, and uniformly dispersing at a high speed; peeling off the first layer of the acrylate pressure-sensitive adhesive layer, and then applying the adhesive to the glazing transfer coating. The first layer of the acrylate pressure-sensitive adhesive layer has a dry glue thickness of 10 μm and is cured at 115-135 ° C to obtain a frost-resistant acrylate pressure-sensitive adhesive label having two layers of glue overlapping.

Example 3

1) First, 2.1 parts of benzoyl peroxide (BPO) was dissolved in 70 parts of ethyl acetate, and stirred well to dissolve evenly. After the dissolution was completed, 40 parts of isooctyl acrylate and butyl acrylate were added. 150 parts of ester, 70 parts of 2-ethylhexyl acrylate, 90 parts of acrylic acid, 30 parts of hydroxyethyl acrylate, 5 parts of vinyl acetate, and 450 parts of toluene were stirred and mixed uniformly.

2) 50 parts of ethyl acetate was added to the reactor to raise the temperature to 75 ° C, after the reflux was stabilized, the 1/2 of the above mixture was slowly added dropwise, and the dropwise addition was completed in 1.5 hours; and the reaction temperature was controlled at 80-82 ° C; Then add 30 parts of ethyl acetate dissolved in 0.8 parts of benzoyl peroxide (BPO), add dropwise in 15 minutes, and keep the reaction for 1.2 hours; then slowly add the remaining 1/2 monomer mixture, The dropping time is 2.0 hours, the reaction temperature is controlled at 80-82 ° C; then 30 parts of ethyl acetate dissolved in 0.8 parts of benzoyl peroxide (BPO) is added dropwise, and the dropwise addition is completed within 15 minutes, and the reaction is kept for 1 hour; Further, 20 parts of ethyl acetate in which 0.8 part of benzoyl peroxide (BPO) was dissolved was added dropwise thereto, and the mixture was added dropwise over 15 minutes. After the completion of the dropwise addition, the mixture was reacted at 80 ° C for two hours to obtain a freeze-resistant acrylate pressure-sensitive adhesive.

Application Example 3

1) 100 parts by weight of the pressure-sensitive adhesive prepared above, adding 0.25 parts by weight of an epoxy resin and 0.2 parts of an isocyanate curing agent, dispersing at a high speed, uniformly spreading, and transferring to a subsurface synthetic paper through a glassy base paper (PP) On the synthetic paper, the dry glue thickness was 33 μm, and it was cured at 115-135 ° C to obtain a first layer of acrylate pressure-sensitive adhesive layer, which was placed in a baking oven at 60 ° C for 72 hours.

2) Taking 100 parts by weight of the pressure-sensitive adhesive prepared above, uniformly dispersing and stirring at a high speed; peeling off the first layer of the acrylate pressure-sensitive adhesive layer, and then applying the adhesive to the first layer by applying a transfer coating The adhesive surface of the acrylate pressure-sensitive adhesive layer has a dry glue thickness of 12 μm and is cured at 115-135 ° C to obtain a frost-resistant acrylate pressure-sensitive adhesive label having two layers of glue overlapping.

The performance of the freeze-resistant acrylate pressure-sensitive adhesive label: the initial adhesion is 15# steel ball; the blood-filling tube has no lifting, opening, etc., and the blood bag of -30 °C has no lifting phenomenon.

The above embodiments are merely preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention belong to the present invention. The scope of the claim.

Claims

A freeze-resistant acrylate pressure-sensitive adhesive characterized by being subjected to radical polymerization of a comonomer, the comonomer comprising:

20-50 parts by weight of isooctyl acrylate,

Butyl acrylate 150-200 parts by weight,

50-100 parts by weight of acrylic acid,

2-70 parts by weight of 2-ethylhexyl acrylate

Ethyl acetate 100-200 parts by weight,

Toluene 300-450 parts by weight,

3-5 parts by weight of benzoyl peroxide.
The freeze-resistant acrylate pressure-sensitive adhesive according to claim 1, wherein the comonomer comprises:

30-40 parts by weight of isooctyl acrylate,

Butyl acrylate 160-180 parts by weight,

60-80 parts by weight of acrylic acid,

2-ethylhexyl acrylate 20-70 parts by weight,

Ethyl acetate 120-150 parts by weight,

Toluene 350-400 parts by weight,

4-5 parts by weight of benzoyl peroxide.
The freeze-resistant acrylate pressure-sensitive adhesive according to claim 1 or 2, wherein the comonomer further comprises 0 to 70 parts by weight of vinyl acetate.
The acrylate pressure-sensitive adhesive according to claim 1 or 2, wherein the comonomer further comprises 20 to 50 parts by weight of hydroxyethyl acrylate.
A method for preparing a freeze-resistant acrylate pressure-sensitive adhesive according to claim 1, wherein the preparation method comprises the following steps:

1) Dissolve 1-2.6 parts by weight of benzoyl peroxide in 40-60 parts by weight of ethyl acetate, and then add a formula amount of isooctyl acrylate, butyl acrylate, acrylic acid, 2-ethylhexyl acrylate And toluene, stir and mix well to obtain a mixed solution;

2) 30-50 parts by weight of ethyl acetate is added to the reactor to raise the temperature to 76-80 ° C, after the reflux is stabilized, slowly start adding 1/2 volume of the above mixture, and react at 80-82 ° C for 1-1.5 hours;

3) in the step 2) while the remaining benzoyl peroxide is dissolved in the remaining ethyl acetate, divided into 10-30 parts by weight of three parts of benzoyl peroxide in ethyl acetate solution; one of them Adding to the reaction system of step 2), holding for 1 hour; then slowly adding the remaining 1/2 volume of the mixed solution to the reaction system at a reaction temperature of 80-82 ° C, the dropping time is controlled at 2-3 After the completion of the dropwise addition, a portion of ethyl acetate solution of benzoyl peroxide was continuously added to the reaction system, and the reaction was kept for 1 hour, and the last ethyl acetate solution of benzoyl peroxide was added dropwise again. The reaction was carried out at a constant temperature of 80 ° C for 1.5 to 2.5 hours to obtain an acrylate pressure-sensitive adhesive which was subjected to freezing.
A freeze-resistant acrylate pressure-sensitive adhesive label produced by using the freeze-resistant acrylate pressure-sensitive adhesive of claim 1.
A method for preparing a freeze-resistant acrylate pressure-sensitive adhesive label, characterized in that the preparation method comprises the following steps:

A) In the acrylate pressure-sensitive adhesive according to any one of claims 1 to 4, a curing agent is added in a ratio of a mass ratio of the acrylate pressure-sensitive adhesive to the curing agent of 100: (0.1 - 0.5), and the dispersion is uniformly stirred. After being coated on a silicone oil base paper, curing at 115-135 ° C to form a cured adhesive layer, and then attaching a film substrate on the surface of the adhesive layer, and placing it in a baking oven to obtain a first layer of acrylic pressure-sensitive adhesive layer;

B) The acrylate pressure sensitive adhesive according to claim 1, which is coated on a silicone oil base paper and cured at 115-135 ° C to obtain a second layer of acrylate pressure-sensitive adhesive layer;

C) removing the silicone oil base paper in the first layer of the acrylic pressure-sensitive adhesive layer described in the step A) to expose the cured adhesive layer, and then laminating the second layer of the acrylate pressure-sensitive adhesive layer of the step B) on the cured adhesive layer. A freeze-resistant pressure sensitive adhesive label is produced.
The production method according to claim 7, wherein the curing agent is a mixture of an isocyanate and an epoxy resin, and the mass ratio of the two is 1:1.
The preparation method according to claim 7, wherein the silicone oil bottom paper is one of glassine silicone oil bottom paper, PET silicone oil bottom paper, and PP silicone oil bottom paper; the film substrate is PET, BOPP, One of PP and PE.
The preparation method according to claim 7, wherein the cured adhesive layer has a thickness of 30 to 35 μm; and the freeze-resistant pressure-sensitive adhesive label has a total thickness of 40 to 55 μm.