CN109749671B - Acrylate pressure-sensitive adhesive containing nano siloxane condensate, adhesive sheet and preparation method thereof - Google Patents
Acrylate pressure-sensitive adhesive containing nano siloxane condensate, adhesive sheet and preparation method thereof Download PDFInfo
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Abstract
The invention provides a pressure-sensitive adhesive, which comprises the reaction product of the following reaction components in parts by weight based on 100 parts by weight of the total weight of an acrylate copolymer A and a nano siloxane condensate B: 1)90-99 parts by weight of an acrylate copolymer A, wherein the acrylate copolymer A is copolymerized by an acrylate monomer mixture containing at least one carboxyl-containing monomer P; 2)1-10 parts by weight of nano siloxane condensate B, wherein the nano siloxane condensate B is a partial or complete cocondensate product comprising a siloxane compound B1, a siloxane compound B2 and a siloxane compound B3, and the B1 is a siloxane compound containing carboxylic acid group functional groups; the B2 is a siloxane compound containing an alkyl functional group; the B3 is orthosilicate, and the weight ratio of the siloxane compound B1 to the siloxane compound B2 is 1:10-20: 1; 3)5 to 15 parts of petroleum hydrocarbon tackifying resin and 4)0.02 to 2 parts of cross-linking agent. The pressure sensitive adhesive has strong adhesion to low energy surfaces.
Description
Technical Field
The invention relates to the field of pressure-sensitive adhesive, in particular to an acrylate pressure-sensitive adhesive, an adhesive sheet and a preparation method thereof.
Background
With the development of manufacturing industry, plastics and recycled plastics, especially thermoplastic polyolefins, have lower cost and stronger processability than metal materials used in the past, and thus are increasingly applied in the fields of automobile manufacturing, commercial labels, electronic devices, and the like. However, this also presents a significant challenge to conventional bonding techniques because these materials tend to have low surface energies and bonding is relatively difficult. Although rubber adhesives generally have good adhesion to low energy surfaces, the low aging resistance of rubber is often a concern in use. The acrylate adhesive has moderate cost and excellent ageing resistance, so that acrylate adhesive tape products for adhering to low-energy surfaces are successfully developed.
Recently, the use of surface-modified silica particles as additives in acrylate pressure-sensitive adhesives to increase their adhesive properties has been increasing. US6586483 (g.g. johnson et al) discloses a foam comprising surface modified nanoparticles, surface modified silica particles being used as foam stabilizers added to adhesive foam; WO200665373( affluence) uses surface modified silica particles to increase the stability of optical pressure sensitive adhesives in high temperature and high humidity environments; WO2011133331 (Sierke. D. Michelnique, etc.) uses surface modified silica particles to increase cohesive force of pressure-sensitive adhesive, WO2014186316 (J. Hemifik, etc.) uses surface modified silica particles to increase comprehensive adhesive property of pressure-sensitive adhesive on medium and low energy surfaces, which provides a new technical means for solving the problem of adhesion of acrylate pressure-sensitive adhesive on low energy surfaces. In particular, WO201212060 (chen et al) discloses a pressure sensitive adhesive containing modified silica nanoparticles on the surface, which has good anti-slip properties on low energy surfaces.
Disclosure of Invention
The invention aims to provide an acrylate pressure-sensitive adhesive containing a nano siloxane condensate B so as to meet the requirement of strong adhesion with a low-energy surface.
According to one aspect of the present invention, there is provided a pressure sensitive adhesive comprising the reaction product of the following reaction components: 1)90-99 parts by weight of an acrylate copolymer A, based on 100 parts by weight of the total weight of the acrylate copolymer A and a nano siloxane condensate B, the acrylate copolymer A is formed by copolymerizing a mixture of acrylate monomers, the acrylate monomer mixture at least contains one carboxyl-containing monomer P, and the weight part of the carboxyl-containing monomer P is 1-10 parts by weight based on 100 parts by weight of the acrylate monomer mixture; 2)1-10 parts by weight of a nano siloxane condensate B, based on 100 parts by weight of the total weight of the acrylate copolymer A and the nano siloxane condensate B, the nano siloxane condensate B being a partial or total co-condensation product comprising a siloxane compound B1, a siloxane compound B2, and a siloxane compound B3, the siloxane compound B1 having the general formula I: (RO)3-Si-(CH2)a-R1-(CH2)b-COOH (I) wherein 1. ltoreq. a.ltoreq.4; b is more than or equal to 1 and less than or equal to 12, R1Represents an amide group (- (CO) -NH-) or an ester group (- (CO) -O-), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; the siloxane compound B2 has the general formula II: r2 cSi(OR)4-c(II) wherein c is not less than 1 and not more than 3, R2Represents at least one linear, branched or cyclic alkyl group having a carbon number of 1 to 20, R represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4; the weight ratio of the siloxane compound B1 to the siloxane compound B2 is 1:10-20: 1; the siloxane compound B3 has the general formula III: si (OR)4(III) wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; 3)5 to 15 parts of petroleum hydrocarbon tackifying resin by weight, based on the total weight of the acrylate copolymer A and the nano siloxane condensate B as 100 parts by weight, and 4)0.02 to 2 parts of cross-linking agent by weight, based on the total weight of the acrylate copolymer A and the nano siloxane condensate B as 100 parts by weight.
According to another aspect of the present invention, there is provided a pressure-sensitive adhesive sheet comprising a substrate and a dried coating applied on the substrate, the dried coating comprising a coating obtained by applying the pressure-sensitive adhesive to the surface of the substrate, and drying and curing the applied pressure-sensitive adhesive.
According to another aspect of the present invention, there is provided a method for producing a pressure-sensitive adhesive sheet, comprising the steps of: and applying the pressure-sensitive adhesive on the surface of the base material to form a wet pressure-sensitive adhesive liquid film on the surface of the base material, and drying and curing the wet pressure-sensitive adhesive liquid film to obtain a dry coating, wherein the dry coating is attached to the surface of the base material.
The above summary is not intended to describe each disclosed embodiment of every implementation of the present invention. The features and advantages of the above and further embodiments of the present invention will become more apparent by describing in greater detail exemplary embodiments thereof with reference to the accompanying drawings and detailed description.
Detailed Description
It is to be understood that other various embodiments can be devised and modified by those skilled in the art in light of the teachings herein without departing from the scope or spirit of the invention. The following detailed description is, therefore, not to be taken in a limiting sense.
Unless otherwise indicated, all numbers expressing feature sizes, quantities, and physical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1, 2, 3, 4, and 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
Pressure-sensitive adhesive
The pressure-sensitive adhesive provided by the invention can form a compact transparent pressure-sensitive adhesive coating on the surface of a substrate, and comprises the reaction product of the following reaction components: 1)90-99 parts by weight of an acrylate copolymer A, based on 100 parts by weight of the total weight of the acrylate copolymer A and a nano siloxane condensate B, the acrylate copolymer A is formed by copolymerizing a mixture of acrylate monomers, the acrylate monomer mixture at least contains one carboxyl-containing monomer P, and the weight part of the carboxyl-containing monomer P is 1-10 parts by weight based on 100 parts by weight of the acrylate monomer mixture; 2)1-10 parts by weight of a nano siloxane condensate B, based on 100 parts by weight of the total weight of the acrylate copolymer A and the nano siloxane condensate B, the nano siloxane condensate B being a partial or total co-condensation product comprising a siloxane compound B1, a siloxane compound B2, and a siloxane compound B3, the siloxane compound B1 having the general formula I: (RO)3-Si-(CH2)a-R1-(CH2)b-COOH (I) wherein 1. ltoreq. a.ltoreq.4; b is more than or equal to 1 and less than or equal to 12, R1Represents an amide group or an ester group, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; the siloxane compound B2 has the general formula II: r2 cSi(OR)4-c(II) wherein c is not less than 1 and not more than 3, R2Represents at least one linear, branched or cyclic alkyl group having a carbon number of 1 to 20, R represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4; the weight ratio of the siloxane compound B1 to the siloxane compound B2 is 1:10-20: 1; the siloxane compound B3 has the general formula III: si (OR)4(III) wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; 3)5 to 15 parts of petroleum hydrocarbon tackifying resin by weight, based on the total weight of the acrylate copolymer A and the nano siloxane condensate B as 100 parts by weight, and 4)0.02 to 2 parts of cross-linking agent by weight, based on the total weight of the acrylate copolymer A and the nano siloxane condensate B as 100 parts by weight.
The mixture of acrylate monomers includes one or more of the following: an alkyl acrylate monomer M, (meth) acrylate monomer N, said alkyl acrylate monomer M having a glass transition temperature of less than-40 ℃ polymerized to form a homopolymer and said acrylate monomer having a glass transition temperature of greater than 0 ℃ polymerized to form a homopolymer. The alkyl acrylate monomer M is present in an amount of 40 to 99 parts by weight, preferably 70 to 90 parts by weight, based on 100 parts by weight of the mixture of the acrylate monomers. If the weight part of the alkyl acrylate monomer M is less than 40, the initial adhesion of the prepared acrylic pressure-sensitive adhesive is insufficient, and the viscosity is low; if the alkyl acrylate monomer M is present in an amount of more than 99 parts by weight, the resultant acrylic pressure-sensitive adhesive will have insufficient cohesive force and will be susceptible to cohesive failure. The (meth) acrylate monomer N is present in an amount of 0 to 50 parts by weight, preferably 2 to 40 parts by weight, based on 100 parts by weight of the mixture of the acrylate monomers. If the weight part of the (meth) acrylic ester N is more than 50, the resulting acrylic pressure-sensitive adhesive has insufficient initial tack and very low tackiness. The mixture of acrylate monomers may also include a carboxyl group-containing monomer P. The acrylic monomer P is present in an amount of 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the mixture of acrylic ester monomers. If the weight part of the acrylic monomer P is less than 1, the resulting pressure-sensitive adhesive composition cannot obtain sufficient cohesive force through crosslinking, and cohesive failure is liable to occur; if the acrylic monomer P is more than 10 parts by weight, the polarity of the acrylic copolymer becomes too high due to the addition of too much carboxyl group-containing monomer P, which is disadvantageous for adhesion to a low energy surface, and the resulting pressure-sensitive adhesive sheet has low tackiness on a PP sheet.
The nano siloxane condensate B accounts for 1-10 parts by weight, and if the total weight of the acrylate copolymer A and the nano siloxane condensate B is less than 1 part by weight, the high-temperature static shearing duration of the prepared pressure-sensitive adhesive bonding sheet on a PP plate is short, and the pressure-sensitive adhesive bonding sheet is very easy to slip off the PP plate; if the nano silicone condensate B is present in an amount of more than 10 parts by weight, the resulting pressure-sensitive adhesive composition may not be crosslinked to obtain sufficient cohesive force, and cohesive failure may easily occur.
The weight part of the petroleum hydrocarbon tackifying resin is 5-15 parts, the total weight of the acrylate copolymer A and the nano siloxane condensate B is 100 parts, and if the weight of the contained hydrocarbon petroleum tackifying resin is less than 5 parts, the high-temperature static shearing duration of the prepared pressure-sensitive adhesive bonding sheet on a PP plate is very short, and the pressure-sensitive adhesive bonding sheet is very easy to slide off the PP plate; if the hydrocarbon petroleum-based tackifying resin is contained in an amount of more than 15 parts by weight, the resultant pressure-sensitive adhesive sheet has a glass transition temperature that is too high to be peeled off from the PP sheet and slips, and the resultant pressure-sensitive adhesive composition cannot obtain sufficient cohesive force by crosslinking and tends to suffer cohesive failure.
The crosslinking agent is not particularly limited as long as it can react with the acrylate copolymer a and the nano siloxane condensate B, and may be, for example, polyfunctional aziridine, peroxide, benzophenone, triazine, siloxane compound, diacrylate, triacrylate, tetraacrylate, isocyanate and/or epoxy compound.
The pressure-sensitive adhesive of the present invention may further include a solvent, which may be particularly limited as long as it can dissolve the acrylate copolymer a and the nano-siloxane condensate B, and may be, for example, ethyl acetate, butyl acetate, toluene, xylene, butanone, acetone, ethanol, and/or isopropanol.
Pressure-sensitive adhesive sheet and method for producing the same
The invention provides a pressure-sensitive adhesive bonding sheet, which comprises a substrate and a pressure-sensitive adhesive bonding agent drying coating applied on the substrate. The pressure-sensitive adhesive coating comprises a coating obtained by drying and curing the pressure-sensitive adhesive provided by the invention. The pressure sensitive adhesive coating is completely or partially solvent free, preferably completely solvent free.
The details of the pressure-sensitive adhesive are described in the present specification "Pressure-sensitive adhesive"part(s)". The adhesive has a strong bonding force to low energy surfaces.
The present invention provides a method for producing a pressure-sensitive adhesive sheet, comprising the steps of:
the pressure-sensitive adhesive provided by the invention is applied to the surface of the base material, a wet pressure-sensitive adhesive liquid film is formed on the surface of the base material, and the wet pressure-sensitive adhesive liquid film is dried and cured to obtain a dry coating which is attached to the surface of the base material. The details of the pressure-sensitive adhesive are described in the present specification "Pressure-sensitive adhesive bonding Agent for treating cancer"part(s)". The pressure sensitive adhesive may be applied to the surface of the substrate by methods known in the art, which may preferably be one or more of the following: roll coating, flow coating, dip coating, spin coating, spray coating, blade coating, and die coating. The pressure sensitive adhesive coating is completely or partially solvent free, preferably completely solvent free. The pressure sensitive adhesive coating may have any thickness as desired, for example the thickness may range from 2 to 250, preferably from 10 to 100 μm. The pressure-sensitive adhesive patch may be dry-cured using a suitable dry-curing method known in the art. Substrates coated with pressure sensitive adhesives are typically dry cured at room temperature or at elevated temperatures (e.g., temperatures may range from 20 ℃ to 200 ℃, or 80 ℃ to 120 ℃).
Any suitable substrate may be used. The substrate may be of a plastic material, such as polyethylene, polypropylene (including isotactic polypropylene), polystyrene, polyester, polyvinyl alcohol, poly (ethylene terephthalate), poly (butylene terephthalate), a metallized plastic material or a metallized non-woven fabric, a metal foil or a composite film of a metal foil and a plastic material, or foam, such as acrylic foam, polyethylene foam, polyurethane foam, neoprene foam, or the like. The foam can be co-extruded with the glue or can be attached to one or both sides of the foam.
The pressure sensitive adhesive has good bonding properties to low energy surface substrates.
The present invention provides various preferred embodiments regarding a pressure-sensitive adhesive, a pressure-sensitive adhesive sheet, and a method for producing the same.
Preferred embodiment 1 is a pressure-sensitive adhesive comprising the reaction product of the following reaction components:
1)90-99 parts by weight of an acrylate copolymer A, based on 100 parts by weight of the total weight of the acrylate copolymer A and a nano siloxane condensate B, the acrylate copolymer A is formed by copolymerizing an acrylate monomer mixture, the acrylate monomer mixture at least contains one carboxyl-containing monomer P, and the weight part of the carboxyl-containing monomer P is 1-10 parts by weight based on 100 parts by weight of the acrylate monomer mixture;
2)1-10 parts by weight of a nano siloxane condensate B, based on 100 parts by weight of the total weight of the acrylate copolymer A and the nano siloxane condensate B, the nano siloxane condensate B is a partial or total cocondensate comprising a siloxane compound B1, a siloxane compound B2 and a siloxane compound B3, the siloxane compound B1 has the general formula I:
(RO)3-Si-(CH2)a-R1-(CH2)b-COOH (I)
wherein a is more than or equal to 1 and less than or equal to 4; b is more than or equal to 1 and less than or equal to 12, R1Represents an amide group or an ester group, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
the siloxane compound B2 has the general formula II:
R2 cSi(OR)4-c (II)
wherein c is more than or equal to 1 and less than or equal to 3, R2Represents at least one linear, saturated or cyclic alkyl group having a carbon number of 1 to 20, R represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4;
the weight ratio of the siloxane compound B1 to the siloxane compound B2 is 1:10-20: 1;
the siloxane compound B3 has the general formula III:
Si(OR)4(III) wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
3)5 to 15 parts by weight of petroleum hydrocarbon tackifying resin based on 100 parts by weight of the total weight of the acrylate copolymer A and the nano siloxane condensate B, and
4)0.02-2 parts by weight of a cross-linking agent, based on 100 parts by weight of the total weight of the acrylate copolymer A and the nano siloxane condensate B.
Preferred embodiment 2 is the pressure sensitive adhesive of preferred embodiment 1, wherein the mixture of acrylate monomers comprises one or more of the following: an alkyl acrylate monomer M, (meth) acrylate monomer N, said alkyl acrylate monomer M having a glass transition temperature of less than-40 ℃ polymerized to form a homopolymer and said acrylate monomer having a glass transition temperature of greater than 0 ℃ polymerized to form a homopolymer.
Preferred embodiment 3 is the pressure-sensitive adhesive according to preferred embodiment 2, wherein the alkyl acrylate monomer M is present in an amount of 40 to 99 parts by weight based on 100 parts by weight of the mixture of the acrylate monomers.
Preferred embodiment 4 is the pressure-sensitive adhesive of preferred embodiment 3, wherein the alkyl acrylate monomer M is 70 to 90 parts by weight based on 100 parts by weight of the mixture of the acrylate monomers.
Preferred embodiment 5 is the pressure-sensitive adhesive of preferred embodiment 2, wherein the (meth) acrylate monomer N is 0 to 50 parts by weight based on 100 parts by weight of the mixture of the acrylate monomers.
Preferred embodiment 6 is the pressure-sensitive adhesive of preferred embodiment 5, wherein the (meth) acrylate monomer N is 2 to 40 parts by weight based on 100 parts by weight of the mixture of the acrylate monomers.
Preferred embodiment 7 is the pressure-sensitive adhesive of preferred embodiment 2, wherein the acrylic monomer P is present in an amount of 1 to 10 parts by weight based on 100 parts by weight of the mixture of the acrylic ester monomers.
Preferred embodiment 8 is the pressure-sensitive adhesive of preferred embodiment 7, wherein the acrylic monomer P is present in an amount of 2 to 5 parts by weight based on 100 parts by weight of the mixture of the acrylic ester monomers.
Preferred embodiment 9 is the pressure-sensitive adhesive according to preferred embodiment 1, wherein the carboxyl group-containing monomer P is acrylic acid.
Preferred embodiment 10 is the pressure-sensitive adhesive of preferred embodiment 1, wherein the crosslinking agent comprises one or more of the following crosslinking agents: polyfunctional aziridines, peroxides, benzophenones, triazines, siloxane compounds, diacrylates, triacrylates, tetraacrylates, isocyanates, epoxy compounds. Thermal or ultraviolet radiation is a necessary condition to trigger the reaction of the crosslinking agent.
Preferred embodiment 11 a pressure-sensitive adhesive as described in preferred embodiment 1, further comprising a solvent comprising one or more of the following solvents: ethyl acetate, butyl acetate, toluene, xylene, butanone, acetone, ethanol, isopropanol.
Preferred embodiment 12 is a pressure-sensitive adhesive sheet comprising a substrate and a dried coating layer applied on the substrate, the dried coating layer comprising a coating layer obtained by applying the pressure-sensitive adhesive according to preferred embodiments 1 to 11 to the surface of the substrate, and drying and curing the applied pressure-sensitive adhesive.
Preferred embodiment 13 is the pressure-sensitive adhesive sheet as defined in preferred embodiment 12, wherein the substrate comprises one or more of the following group: synthetic resin films, rubber sheets, paper, fabrics, nonwoven fabrics, foam sheets, metal foils, and laminates of the substrates.
Preferred embodiment 14 is a method for producing a pressure-sensitive adhesive sheet, comprising the steps of: the pressure-sensitive adhesive according to preferred embodiments 1 to 11 is applied to the surface of the substrate to form a wet pressure-sensitive adhesive liquid film on the surface of the substrate, and the wet pressure-sensitive adhesive liquid film is dried and cured to obtain a dry coating layer, and the dry coating layer is attached to the surface of the substrate.
Preferred embodiment 15 a method of manufacturing as described in preferred embodiment 14, the pressure sensitive adhesive being applied to the surface of the substrate by: roll coating, flow coating, dip coating, spin coating, spray coating, blade coating, and die coating.
Examples
The following examples and comparative examples are provided to aid in the understanding of the present invention and should not be construed as limiting the scope of the invention. All parts and percentages are by weight unless otherwise indicated.
The raw materials used in the examples of the present invention and the comparative examples are shown in table 1 below.
Table 1 raw materials used in examples and comparative examples
The present invention mainly evaluates the peel force of the pressure-sensitive adhesive sheets provided in examples and comparative examples by a 180 ° room temperature peel force test, and the present invention further evaluates the static shear duration of the pressure-sensitive adhesive sheets provided in examples and comparative examples by a 70 ℃ static shear duration test.
180 degree room temperature peel force test
The 180 ° room temperature peel force test procedure is described in ASTM International Standard D3330. The test was done on an Instron tensile tester with a peel speed of 304.8/min. The used substrate to be adhered is a brand new polypropylene (PP) plate. And tearing off the protective film on one side to expose a fresh surface as an adhered surface. The pressure sensitive adhesive sheet samples were cut into 25.4mm by 200mm tape samples. The sample preparation method comprises the steps of tearing off the release film of the adhesive tape sample to expose the surface to be tested, rolling a 1kg rubber roller back and forth once to adhere the surface to be tested to the surface of a new PP plate, placing the prepared sample to be tested in an environment with the temperature of 23 ℃ and the relative humidity of 60% for 20min, testing, and recording the numerical value of the stripping force.
70 ℃ static shear duration test
The 70 ℃ static shear duration test procedure was as described in ASTM International Standard D3654, loaded with a 1kg load under the test samples and vertically suspended in a 70 ℃ oven. The sample was prepared by sampling 25.4mm by 25.4mm tape. The sample preparation method comprises the steps of tearing off the release film of the adhesive tape sample to expose the surface to be detected, and rolling the adhesive tape sample back and forth by using a 1kg rubber roller to adhere to the surface of a new PP plate once. The time recorded for the test is the duration of time that the sample did not slip off the PP plate under the load. As shown in table 4, the failure mode of the sample was not slip, but cohesive failure due to insufficient cohesive force of the glue layer, and was labeled specifically.
The results of the tests of peel force and static shear duration of the pressure-sensitive adhesive sheets provided in the examples of the present invention and comparative examples are shown in table 4.
Preparation of 4-oxo-4- [ [3- (trimethoxysilyl) propyl ] amino ] -butyric acid (OTMSPABA)
5.00g (50mmol) succinic anhydride was added to a 250 ml round bottom flask and dissolved in 80 ml ethyl acetate. 8.96g (50mmol) of 3-aminopropyltrimethoxysilane were added dropwise to 50 ml of ethyl acetate at room temperature, and after stirring for 4 hours, the resulting solution was filtered to remove a white solid. After ethyl acetate was removed by a rotary evaporator, a pale yellow oily liquid was obtained, and it was confirmed by infrared and 1H nuclear magnetic resonance that 4-oxo-4- [ [3- (trimethoxysilyl) propyl ] amino ] -butyric acid was obtained.
Preparation of samples A1-A6 in acrylate copolymer A
100 parts by weight of the monomers were charged into a glass bottle in the proportions shown in Table 2, 0.2 part by weight of Vazo-67 as an initiator and EA and IPA as shown in the Table, mixed uniformly, and deoxygenated by introducing nitrogen gas for 2 minutes, and then the glass bottle was placed in the reactor in a closed state. The mixture was heated to 65 ℃ and reacted for 24 hours while mixing, to finally obtain an acrylic copolymer having a solid content of about 40%.
TABLE 2 monomer composition of acrylate copolymer A
| Samples | 2-EHA | MA | IBOA | BA | AA | EA | IPA |
| A1 | 78 | 19 | 3 | 147 | 3 | ||
| A2 | 86.5 | 11 | 2.5 | 150 | |||
| A3 | 90 | 10 | 150 | ||||
| A4 | 9 | 90 | 1 | 150 | |||
| A5 | 88 | 12 | 150 | ||||
| A6 | 9.5 | 90 | 0.5 | 147 | 3 |
Preparation of samples B (i) -B (iii) in nanosiloxane condensate B
Sample b (i): 5.0g tetraethyl orthosilicate was dissolved in 41.5g isopropanol at room temperature, then during stirring 0.5g hexadecyltrimethoxysilane and 0.5g 4-oxo-4- [ [3- (triethoxysilyl) propyl ] amino ] -butyric acid were added, stirring was continued for 1h, 2.5g deionized water was added, and 0.5g hydrochloric acid (0.1mol/L) was added dropwise, a clear and homogeneous solution was obtained at different reaction times after mixing was completed.
Sample b (ii): the procedure is as in sample B (i) except that hexadecyltrimethoxysilane is replaced by n-octyltrimethoxysilane.
Sample b (iii): the procedure is as for sample B (i) except that tetraethyl orthosilicate and 4-oxo-4- [ [3- (trimethoxysilyl) propyl ] amino ] -butyric acid are substituted with tetramethyl orthosilicate and 4-oxo-4- [ [3- (triethoxysilyl) propyl ] amino ] -butyric acid, respectively.
Preparation of pressure-sensitive adhesive sheet E1-E34
After the nanosiloxane condensate B (i) had started to react for 44 hours, 112 hours and 205 hours, 95 parts by weight of A1, 5 parts by weight of B (i), 7.2 parts by weight of Regalrez 1126, 0.0012 parts by weight of RD1054 and a certain amount of toluene were mixed homogeneously to give a pressure-sensitive adhesive solution having a solids content of 20%. The pressure-sensitive adhesive solution was coated on the surface of a 50 μm-thick PET film, baked at 105 ℃ for 5min to give a 50 μm-thick adhesive layer, and a 38 μm-thick PET release film was coated thereon, and the pressure-sensitive adhesive sheet sample thus obtained was designated as example E1-E3.
The procedure for preparing examples E4-38 and comparative examples CE1-22 was substantially the same as that for preparing example E1, except that the reaction time and the parts by weight of the acrylic copolymer A and the nanosiloxane condensate B, the type of tackifying resin, and the parts by weight of crosslinking agent (as shown in Table 3) were different from those of example 1.
TABLE 3 weight Components of examples E1-38 and comparative CE1-22
TABLE 4 evaluation of the Performance of examples E1-38 and comparative examples CE1-22
Examples E1-E38 show that, when the AA monomer is contained in an amount of 1 part to 10 parts by weight based on 100 parts by weight of the acrylic copolymer A, the pressure-sensitive adhesive sheet obtained has good peel force on a PP sheet and high-temperature static shear duration. Comparative example CE19 shows that when the weight part of AA-containing monomer is less than 1 part by weight based on 100 parts by weight of the acrylic copolymer A, the resulting pressure-sensitive adhesive composition cannot obtain sufficient cohesive force by crosslinking. Comparative example CE18 shows that when the weight part of the AA-containing monomer is more than 10 parts based on 100 parts by weight of the acrylic copolymer A, the resulting pressure-sensitive adhesive sheet has a low tackiness on a PP sheet. This is because too much AA added makes the acrylic copolymer too polar to bond to low energy surfaces.
Examples E1-E38 show that, in the pressure-sensitive adhesive composition, when the nanosiloxane condensate B is contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the total weight of the acrylic copolymer a and the nanosiloxane condensate B, the pressure-sensitive adhesive sheet produced has good peel force and high-temperature static shear duration on a PP plate. Comparative examples CE1,4,5,11,17 show that if the nano-siloxane condensate B is contained in an amount of less than 1 part by weight, the pressure-sensitive adhesive sheet produced has a short duration of high-temperature static shear on the PP plate and is very liable to slip off the PP plate. Comparative example CE2-3 shows that if the nano-siloxane condensate B is contained in an amount of more than 10 parts by weight, the resulting pressure-sensitive adhesive composition cannot obtain sufficient cohesive force by crosslinking.
Examples E1-E38 show that, in the pressure-sensitive adhesive composition, when the hydrocarbon petroleum-based tackifying resin is contained in an amount of 5 to 15 parts by weight based on 100 parts by weight of the total weight of the acrylic copolymer and the nano-siloxane condensate B, the pressure-sensitive adhesive sheet produced has good peel force and high-temperature static shear duration on a PP plate. Comparative example CE6 shows that when the hydrocarbon petroleum based tackifying resin is contained in an amount of less than 5 parts by weight, the high-temperature static shear on a PP sheet lasts for a short period of time and is liable to slip off the PP sheet. Comparative example CE7 shows that if the hydrocarbon petroleum-based tackifying resin is contained in an amount of more than 15 parts by weight, the resultant pressure-sensitive adhesive sheet has a glass transition temperature that is too high, and slips when peeled from a PP sheet, and the resultant pressure-sensitive adhesive composition cannot obtain sufficient cohesive force by crosslinking.
Although the foregoing detailed description contains many specific details for the purpose of illustration, it will be appreciated by those of ordinary skill in the art that numerous variations, alterations, substitutions and alterations to these details are within the scope of the invention as claimed. Therefore, the disclosure described in the detailed description does not impose any limitation on the invention as claimed. The proper scope of the invention should be determined by the appended claims and their proper legal equivalents. All cited references are incorporated herein by reference in their entirety.
Claims (14)
1. A pressure sensitive adhesive comprising the reaction product of the following reaction components:
1)90-99 parts by weight of an acrylate copolymer A, based on 100 parts by weight of the total weight of the acrylate copolymer A and a nano siloxane condensate B, the acrylate copolymer A is formed by copolymerizing an acrylate monomer mixture, the acrylate monomer mixture at least contains one carboxyl-containing monomer P, and the weight part of the carboxyl-containing monomer P is 1-10 parts by weight based on 100 parts by weight of the acrylate monomer mixture;
2)1-10 parts by weight of a nano siloxane condensate B, based on 100 parts by weight of the total weight of the acrylate copolymer A and the nano siloxane condensate B, the nano siloxane condensate B being a partial or total co-condensation product comprising a siloxane compound B1, a siloxane compound B2, and a siloxane compound B3, the siloxane compound B1 having the general formula I:
(RO)3-Si-(CH2)a-R1-(CH2)b-COOH (I)
wherein a is more than or equal to 1 and less than or equal to 4; b is more than or equal to 1 and less than or equal to 12, R1Represents an amide group or an ester group, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
the siloxane compound B2 has the general formula II:
R2 cSi(OR)4-c (II)
wherein c is more than or equal to 1 and less than or equal to 3, R2Represents at least one linear, branched or cyclic alkyl group having a carbon number of 1 to 20, R represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4;
the weight ratio of the siloxane compound B1 to the siloxane compound B2 is 1:10-20: 1;
the siloxane compound B3 has the general formula III:
Si(OR)4 (III)
wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
3)5 to 15 parts by weight of petroleum hydrocarbon tackifying resin based on 100 parts by weight of the total weight of the acrylate copolymer A and the nano siloxane condensate B, and
4)0.02-2 parts by weight of a cross-linking agent, based on 100 parts by weight of the total weight of the acrylate copolymer A and the nano siloxane condensate B.
2. The pressure sensitive adhesive of claim 1 wherein the acrylate monomer mixture comprises one or more of: an alkyl acrylate monomer M, a (meth) acrylate monomer N, said alkyl acrylate monomer M polymerized to a homopolymer having a glass transition temperature of less than-40 ℃, said (meth) acrylate monomer N polymerized to a homopolymer having a glass transition temperature of greater than 0 ℃.
3. The pressure-sensitive adhesive according to claim 2, wherein the alkyl acrylate monomer M is present in an amount of 40 to 99 parts by weight based on 100 parts by weight of the mixture of the acrylate monomers.
4. The pressure-sensitive adhesive according to claim 3, wherein the alkyl acrylate monomer M is present in an amount of 70 to 90 parts by weight based on 100 parts by weight of the mixture of the acrylate monomers.
5. The pressure-sensitive adhesive according to claim 2, wherein the (meth) acrylate monomer N is present in an amount of 0 to 50 parts by weight based on 100 parts by weight of the mixture of the acrylate monomers.
6. The pressure-sensitive adhesive according to claim 5, wherein the (meth) acrylate monomer N is present in an amount of 2 to 40 parts by weight based on 100 parts by weight of the mixture of the acrylate monomers.
7. The pressure-sensitive adhesive according to claim 1, wherein the carboxyl group-containing monomer P is present in an amount of 2 to 5 parts by weight based on 100 parts by weight of the mixture of the acrylate monomers.
8. The pressure-sensitive adhesive according to claim 1, wherein the carboxyl group-containing monomer P is acrylic acid.
9. The pressure sensitive adhesive of claim 1 wherein the crosslinking agent comprises one or more of the following crosslinking agents: polyfunctional aziridines, peroxides, benzophenones, triazines, siloxane compounds, diacrylates, triacrylates, tetraacrylates, isocyanates, epoxy compounds.
10. The pressure sensitive adhesive of claim 1 further comprising a solvent comprising one or more of the following solvents: ethyl acetate, butyl acetate, toluene, xylene, butanone, acetone, ethanol, isopropanol.
11. A pressure-sensitive adhesive sheet comprising a substrate and a dried coating layer applied on the substrate, the dried coating layer comprising a coating layer obtained by applying the pressure-sensitive adhesive as claimed in any one of claims 1 to 10 to the surface of the substrate and drying and curing.
12. The pressure-sensitive adhesive sheet according to claim 11, wherein the substrate comprises one or more of the following group: synthetic resin films, rubber sheets, paper, fabrics, nonwoven fabrics, foam sheets, metal foils, and laminates of the substrates.
13. A method for preparing a pressure-sensitive adhesive laminating sheet comprises the following steps: applying the pressure-sensitive adhesive according to any of claims 1 to 10 to a substrate surface to form a wet pressure-sensitive adhesive film on the substrate surface, and drying and curing the wet pressure-sensitive adhesive film to obtain a dried coating, wherein the dried coating is attached to the substrate surface.
14. The method of claim 13, wherein the pressure sensitive adhesive is applied to the surface of the substrate by: roll coating, flow coating, dip coating, spin coating, spray coating, blade coating, and die coating.
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