CN113997657A - Oleic acid-resistant foam, and preparation method and application thereof - Google Patents

Oleic acid-resistant foam, and preparation method and application thereof Download PDF

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CN113997657A
CN113997657A CN202111171658.5A CN202111171658A CN113997657A CN 113997657 A CN113997657 A CN 113997657A CN 202111171658 A CN202111171658 A CN 202111171658A CN 113997657 A CN113997657 A CN 113997657A
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crosslinking
core material
foam
degree
foam core
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CN113997657B (en
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顾正青
夏有贵
耿洪斌
周奎任
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Suzhou Shinuo New Material Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C08L71/03—Polyepihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Abstract

The invention discloses oleic acid-resistant foam, a preparation method and application thereof; the oleic acid resistant foam comprises a high-crosslinking-degree foam core material, a low-crosslinking-degree foam core material and a bonding layer, the oleic acid resistant foam takes the high-crosslinking-degree foam core material as a center, the low-crosslinking-degree foam core materials on two sides are symmetrically arranged, and the high-crosslinking-degree foam core material and the low-crosslinking-degree foam core material are bonded through the bonding layer, and the oleic acid resistant foam comprises the following steps: s1: preparing a high crosslinking degree foam core material; s2: preparing a low-crosslinking-degree foam core material; s3: the release films on two sides of the high-crosslinking-degree foam core material are torn off, the bonding layers are respectively attached to the two sides, the low-crosslinking-degree foam core material is attached to the other side of each bonding layer, the oleic acid-resistant foam is obtained, the oleic acid-resistant foam adhesive tape can be prepared by attaching the adhesive surface layers to the upper surface and the lower surface of the oil-resistant foam, the oil-resistant acid-resistant foam adhesive tape prepared by the process has good die cutting performance, excellent impact resistance, water resistance, re-peeling performance and the like, and meanwhile has good oleic acid resistance, and the requirements in the electronic field can be met.

Description

Oleic acid-resistant foam, and preparation method and application thereof
Technical Field
The invention relates to the technical field of adhesives, and particularly relates to oleic acid-resistant foam, a preparation method and application thereof.
Background
The foam adhesive tape has excellent wettability, lasting viscosity, weather resistance, water resistance, sealing property, compression deformation resistance, flame retardance and the like, is selected according to different thicknesses and functions, is generally applied to the fields of electronic appliances, mechanical parts, various small household appliances, mobile phone accessories, industrial instruments, computers, peripheral equipment, automobile accessories, audio and video equipment, toys, cosmetics and the like, and has a very wide market. Double-sided tapes for attaching a body and a display to a smart phone, a tablet, or a computer are used as foam tapes, and the foam tapes are required to have high bonding strength while having impact resistance, shear resistance, and water resistance. At present, the foam double-sided adhesive tape is used by a plurality of manufacturers at home and abroad, such as apples, samsung, Huachi, OPPO, VIVO, millet and the like.
The earliest foam double-sided tape applied to the electronic client of the mobile phone is a PE foam double-sided tape, has the advantages of water resistance, high bonding strength and removability, but the anti-buffering performance of the tape is general and cannot meet the performance requirements of increasingly thinned electronic fields; along with the narrow framing development of the mobile phone industry, the requirements on double-sided adhesive tapes for bonding the front glass, the outer frame and the middle frame of the mobile phone are more and more strict, the requirements on the buffering performance of large-screen glass are more and more strong, meanwhile, electronic products such as mobile phones and the like are frequently contacted with fingers in daily life, a riding machine is provided for oleic acid sweat and the like on the surfaces of the fingers to permeate into gaps of the mobile phone, the bonding failure of a mobile phone frame is further caused, and the novel waterproof buffering oleic acid-resistant foam adhesive tape is produced.
At present, foam double-sided adhesive tapes applied to bonding of mobile phone outer frames are mainly a few of 3M, Tesa, Nitto, Anyone and the like, wherein 3M is mainly 864XX series, and is characterized in that a styrene-isoprene-styrene segmented copolymer and acrylate prepolymer blending extrusion process is adopted, so that the foam double-sided adhesive tapes have excellent impact resistance and repeelability, but the die cutting property is poor, and the foam double-sided adhesive tapes do not have oleic acid resistance; tesa adopts acrylic ester foam, and has high storage modulus at normal temperature, good die cutting property and good oil and acid resistance, but has defects of impact resistance and waterproofness; nitto is still in the research and development stage at present, it mainly uses chemical-resistant PSA to foam and laminate and get final product, its main characteristic is that the oil acid resistance is good, but shock resistance and repeelable performance are general; the double-sided foam adhesive tape of Anyong is mainly foamed by polyurethane, has excellent impact resistance and water resistance, does not resist oleic acid, has poor repeelability and cannot meet the heavy industry requirement.
Disclosure of Invention
The invention aims to provide oleic acid-resistant foam, a preparation method and application thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the oleic acid resistant foam comprises a high-crosslinking-degree foam core material, a low-crosslinking-degree foam core material and a bonding layer, the high-crosslinking-degree foam core material is used as the center of the oleic acid resistant foam, the low-crosslinking-degree foam core materials on two sides are symmetrically arranged, and the high-crosslinking-degree foam core material and the low-crosslinking-degree foam core material are bonded through the bonding layer.
As optimization, the materials required by the high-crosslinking-degree foam core material comprise, by weight: 100 parts of epichlorohydrin rubber, 0.3-2 parts of cross-linking agent A, 0.3-1.5 parts of cross-linking agent B, 0.2-2 parts of microsphere filler, 0.5-2 parts of aging agent, 0.1-1 part of light stabilizer, 0.5-2 parts of pigment and 350 parts of solvent 250-.
As optimization, the materials required by the low-crosslinking-degree foam core material comprise, by weight: 100 parts of ternary chlorinated polyether elastomer, 10-20 parts of acrylate block copolymer, 10-30 parts of long-chain alkyl monomer, 0.5-3 parts of functional monomer, 0.1-0.5 part of thermal initiator, 1-2 parts of antioxidant, 0.2-2 parts of microsphere filler, 0.5-2 parts of pigment, 0.5-1.5 parts of curing agent and 600 parts of solvent.
Preferably, the high crosslinking degree foam core material and the low crosslinking degree foam core material microsphere filler are one or more of hollow glass microspheres, expanded perlite, expanded acrylonitrile polymer microspheres and non-expanded acrylonitrile polymer microspheres, the solvent is one or more of toluene, xylene, tetrahydrofuran, cyclohexanone and acetone, and the pigment is one or more of alkaline black slurry, white slurry and colored slurry.
Preferably, the epichlorohydrin rubber is one or more of epichlorohydrin homopolymerized rubber elastomer, binary epichlorohydrin, epichlorohydrin copolymerized rubber elastomer and ternary epichlorohydrin elastomer.
Preferably, the light stabilizer is one or more of o-hydroxybenzophenone, benzotriazole, salicylate, triazine, substituted acrylonitrile and hindered amine, the crosslinking agent A is an amine crosslinking agent and comprises one or more of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, m-phenylenediamine, diaminodiphenylmethane, benzidine and bilateral amino ether, the crosslinking agent B is one or more of hydrogen peroxide, tert-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, azodiisobutyronitrile, azodiisovaleronitrile, azodiisoheptanonitrile, dimethyl azodiisobutyrate and azodicyclohexyl carbonitrile, and the aging agent is octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxy phenylpropionate, One or more of tris (2, 4-di-tert-butylphenyl) phosphite.
Preferably, the acrylate block copolymer is a methyl methacrylate-butyl acrylate-methyl methacrylate block copolymer.
Preferably, the long-chain alkyl monomer is alkyl (meth) acrylate containing 4-10 carbon atoms, and comprises one or more of butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate and n-octyl (meth) acrylate.
Preferably, the curing agent is one or more of isocyanate curing agent, epoxy curing agent and amine curing agent, the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, styrenated phenol, 2, 5-di-tert-butyl hydroquinone, 2' -dimethylene bis- (4-methyl-6-tert-butylphenol), 2, 4-trimethyl-1, 2-dihydroquinoline polymer, octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionate, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and 2-mercaptobenzimidazole.
Preferably, the functional monomer is one or more of (meth) acrylic acid, itaconic acid, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylamide and N-methylolacrylamide.
Preferably, the thermal initiator is one or more of benzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile and azobisisoheptonitrile.
As optimization, the method comprises the following steps:
s1: dissolving epichlorohydrin rubber by using a solvent, adding a microsphere filler, an aging agent, a light stabilizer, a pigment, a crosslinking agent A and a crosslinking agent B, uniformly mixing, removing bubbles, coating on a PET release liner 3, pre-drying at 40-100 ℃, removing the solvent, and baking at 160 ℃ for 5-10min to obtain a high-crosslinking-degree foam core material;
s2: dissolving a ternary chlorinated polyether elastomer and an acrylate block copolymer by using a solvent, heating to 80-90 ℃, introducing nitrogen while stirring to purge the liquid level for 60min, adding a long-chain alkyl monomer, a functional monomer and a thermal initiator, uniformly mixing, reacting for 4h, stopping introducing the nitrogen, adding an antioxidant, cooling, adding a microsphere filler, a pigment and a curing agent, uniformly mixing, removing bubbles, coating on a PET release substrate 3, pre-drying at 40-100 ℃, removing the solvent, and baking at 160 ℃ for 5-10min to obtain a low-crosslinking-degree foam core material;
s3: tearing off release films on two sides of the high-crosslinking-degree foam core material, respectively attaching adhesive layers on the two sides, and attaching the low-crosslinking-degree foam core material to the other sides of the adhesive layers to obtain the oleic acid-resistant foam.
As optimization, the two sides of the low-crosslinking-degree foam core material are subjected to corona treatment, and the dyne value is more than 48 dyn/cm.
Preferably, the oil-resistant acid foam adhesive tape is obtained by tearing off release films on the upper side and the lower side of the oil-resistant acid foam and attaching an adhesive surface layer.
Compared with the prior art, the invention has the following beneficial effects: the ternary chlorohydrin elastomer has high elasticity and flexibility, is second to natural rubber, but has the performances of airtightness, oil resistance, solvent resistance, high temperature resistance, low temperature resistance, ozone resistance, aging resistance and the like which are not possessed by natural rubber, and simultaneously, the side chain contains allyl glyceryl ether obtained by ring-opening polymerization, so that the secondary thermal crosslinking reaction can be carried out.
The ternary epichlorohydrin rubber elastomer is characterized in that a polybasic amine and peroxide mixed crosslinking agent is adopted, amines carry out chloro substitution reaction on ternary epichlorohydrin rubber elastomer molecules, then two epichlorohydrin rubber elastomer macromolecules are bridged to form a linking reaction, the chlorine content is reduced, the peroxides are cracked under heating, radicals are generated to attack C ═ C double bonds on allyl groups, the C ═ C double bonds on the allyl groups on the upper side chains of the epichlorohydrin rubber macromolecules are further linked, network crosslinking is generated, and the high elasticity, the repeelability, the oil resistance, the solvent resistance and the aging resistance of the ternary epichlorohydrin rubber elastomer are greatly improved.
The foam core material with the low crosslinking degree adopts the acrylate modified ternary epichlorohydrin elastomer as a main body, improves the flexibility and the impact resistance of the foam core with the low crosslinking degree, is attached to two sides of the foam core material with the high crosslinking degree, enhances the overall impact resistance of the foam adhesive tape, and gives consideration to the oleic acid resistance.
The high-crosslinking-degree foam cotton core material is used as a middle core material and matched with the polymer microspheres, so that the re-peeling performance and the waterproof performance of the foam cotton core material are greatly improved, and meanwhile, the impact resistance is also improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
Fig. 1 is a laminated structure view of an oleic acid-resistant foam tape.
In the figure: 1-PET release liner 2, 2-adhesive surface layer, 3-low crosslinking degree foam core material, 4-bonding layer, 5-high crosslinking degree foam core material and 6-PET release liner 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Sources of materials in the examples:
materials abbreviations Name of Material Source
H1100 Ternary epichlorohydrin rubber Rion Corp.
CG-102 Ternary epichlorohydrin rubber Japan Kao corporation
Epion301 Ternary epichlorohydrin rubber Japan Kao corporation
TETE Triethylene tetramine Aladdin
EDA Ethylene diamine Aladdin
BPO Benzoyl peroxide Group of traditional Chinese medicines
DCP Dicumyl peroxide Group of traditional Chinese medicines
920DE80d30 Polymeric microspheres Aksu
F-50 Polymeric microspheres Japanese pine oil and fat
1076 Octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionate Basff chemical Limited
168 Tris (2, 4-di-tert-butylphenyl) phosphite Basff chemical Limited
292 Sebacic acid bis (1,2,2,6, 6-pentamethylpiperidinol) ester Basff chemical Limited
B117 Basic black pigments Shanghai cautious chemical Co., Ltd
LA2140 Acrylate block copolymers Couloy, Japan Ltd
2-EHA 2-ethylhexyl acrylate Satellite petrochemistry
HEA Acrylic acid hydroxy ethyl ester Satellite petrochemistry
TOL Industrial toluene Satellite petrochemistry
l-75 Isocyanate curing agent BAYER AG
PET release liner 1 75 μm PET release liner YANGZHOU ALVIN FILM Co.,Ltd.
PET release liner 2 50 μm PET ionPatterned substrate YANGZHOU ALVIN FILM Co.,Ltd.
PET release liner 3 25 μm PET release liner YANGZHOU ALVIN FILM Co.,Ltd.
Taking example a1 as an example:
s1: dissolving the ternary chlorinated polyether elastomer and the acrylate block copolymer by using toluene, heating to 82 ℃, introducing nitrogen while stirring to purge the liquid level for 60min, adding 2-ethyl acrylate, hydroxyethyl acrylate and benzoyl peroxide, uniformly mixing, reacting for 4h, stopping introducing the nitrogen, adding octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl propionate and tris (2, 4-di-tert-butylphenyl) phosphite, cooling, adding polymer microspheres, an alkaline black pigment and an isocyanate curing agent, uniformly mixing, removing bubbles, coating on a PET release substrate 3, pre-drying at 100 ℃, removing a toluene solvent, and baking at 160 ℃ for 10min to obtain the low-crosslinking-degree foam cotton core material.
Examples A1-A3, comparative examples CA1-CA 3: according to the change of the conditions such as the compound and the content in the example A1, the specific content data are shown in Table 1, and the detection data are shown in Table 2.
TABLE 1 Low crosslink foam core for examples A1-A3 and comparative examples CA1-CA4
Figure BDA0003293543950000061
Figure BDA0003293543950000071
TABLE 2 Effect of examples A1-A3 and comparative examples CA1-CA4 on storage modulus and compatibility
Figure BDA0003293543950000072
And (4) conclusion: on the premise of ensuring good system compatibility, the more the acrylate block copolymer is added, the lower the normal-temperature storage modulus, and the impact resistance of the foam adhesive tape is enhanced.
Using example B1 as an example, oleic acid resistant foam was prepared in combination with the low cross-linking foam core prepared in example A2
S1: dissolving a ternary chlorinated polyether elastomer by using toluene, adding polymer microspheres, octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl propionate, tris (2, 4-di-tert-butylphenyl) phosphite, bis (1,2,2,6, 6-pentamethylpiperidinol) sebacate, an alkaline black pigment, triethylene tetramine, ethylenediamine, benzoyl peroxide and dicumyl peroxide, uniformly mixing, removing bubbles, coating the mixture on a PET release substrate 3, pre-drying the mixture at 80 ℃, removing a solvent, and baking the mixture for 8min at 160 ℃ to obtain the high-crosslinking-degree foam core material;
s2: preparing a low-crosslinking-degree foam core material;
s3: tearing off release films on two sides of the high-crosslinking-degree foam core material, respectively attaching adhesive layers produced by the Angzo chemistry to the two sides of the high-crosslinking-degree foam core material, and attaching the low-crosslinking-degree foam core material to the other sides of the adhesive layers (the two sides of the low-crosslinking-degree foam core material are subjected to corona treatment, and the dyne value is more than 48dyn/cm), so as to obtain the oleic acid resistant foam.
S4: tearing off release films on the upper side and the lower side of the oil-resistant acid foam cotton, coating a rubber surface layer produced by an azote chemical process on a PET release substrate, and respectively attaching the rubber surface layer to the upper side and the lower side of the oil-resistant acid foam cotton to obtain the oil-resistant acid foam cotton adhesive tape.
Examples B1-B13, comparative examples CB1-CB 6: the specific content data are shown in Table 3 according to the change of the conditions such as the compounds and the contents in example B1.
TABLE 3 acid foam resistant cotton tapes in examples B1-B13 and comparative examples CB1-CB6
Figure BDA0003293543950000081
Figure BDA0003293543950000091
And (3) detection test:
the performance tests of examples B1-B13 and comparative examples CB1-CB6 are carried out by the following specific test methods, and the test data are shown in Table 4.
Testing the density of the foam: cutting the foam into sample pieces of 10cm by 10cm, weighing M, recording the thickness H of the sample pieces, calculating the density of the foam by using a density formula rho (M/(S H) ═ M/(10H) ═ M/(100H), and testing the average value of the three groups in parallel to obtain the density of the foam.
Gel fraction test: weighing about 0.5g of glue film, and recording weight M1Dissolving with 100g toluene for 24 hr, filtering with 400 mesh metal filter screen, and weighing the weight M of the filter screen before filtering2After filtering the solvent mixed solution, putting the filter screen and residues on the filter screen into a 130 ℃ oven to be baked for 1h to constant weight, then putting the filter screen and the residues into a drying dish to be cooled to room temperature, and weighing M3Finally according to the formula
Figure BDA0003293543950000092
Calculating the gel fraction of the adhesive film; the average value obtained by testing the three groups in parallel is the gel fraction of the adhesive film.
Falling ball impact test: the impact resistance of the strip samples was measured according to ASTM D5628 by applying a 180mm2 loop (outer frame 24.5mm, inner frame 20.5mm, 2.0mm width) sample between a stainless steel sheet (24.5mm 3mm) and a 3mm loop stainless steel sheet (outer frame 40mm, inner frame 20mm), then placing a 6.2Kg weight on top of the bonded article for 10 seconds and then removing before leaving the bonded article at 23 ℃ and 50% Relative Humidity (RH) for 48 h. Next, the bonded article was impacted by dropping 3.00Kg (standard beam + weight) from a height of 100cm using an Instron CEAST9340, and the total impact energy (total energy) required to debond the stainless steel substrate was measured and recorded. Three measurements were made for each example and the average was calculated.
Removability: cutting the sample into rectangles (150mm 60mm, width 0.5mm), then attaching the rectangles on a clean stainless steel plate, staying for 24h at 23 ℃ and 50% Relative Humidity (RH), starting with any part of a stainless steel tweezers, winding the strip-shaped sample at the tip of the tweezers for several circles, peeling off the adhesive tape at 45 degrees, 90 degrees and other angles at a speed of not less than 5 cm/s, wherein the adhesive tape is not broken and no residual adhesive is remained on the steel plate, the re-peeling performance is good, three strips are tested in each example, and any broken or residual adhesive means poor re-peeling performance.
Oil and acid resistance: removing the light release film from the sample wafer, adhering 50 μm POT base film to the adhesive surface, cutting into sample strips of 25mm x 50mm, removing the second release film, slowly adhering the adhesive surface to SUS steel plate, storing at room temperature for 24h, placing the SUS steel plate with foam sample strips in 65 deg.C oleic acid, sealing and storing for 72h, taking out the sample, wiping the residual oleic acid with paper, recovering at room temperature for 2h, and observing the swelling degree and easy falling off of the sample strips
TABLE 4 Effect of examples B1-B13 and comparative examples CB1-CB6 on the properties
Figure BDA0003293543950000101
Figure BDA0003293543950000111
And (4) conclusion: when the tensile strength and the tensile rate of the foam respectively reach more than 3MPa and 600 percent at the same time, the re-peeling performance is usually better, and if the tensile strength or the tensile rate is reduced, the re-peeling performance is also reduced; meanwhile, in the embodiment, when the addition amount of the polymer microspheres is less than 0.2 part, the falling ball impact performance of the foam is poor, and when the addition amount is more than 2 parts, the tensile strength is too low, so that the re-peeling property is poor; in the examples, epichlorohydrin rubber and solvent-resistant PSA facings with better grease resistance are used, but from the actual test results, the crosslinking degree (gel fraction) of the foam also affects the overall oil and acid resistance and impact resistance, when the gel fraction is higher than 70%, the oleic acid resistance and the re-peeling resistance are significantly improved, and the impact resistance is reduced, on the contrary, when the gel fraction is lower than 50%, the oleic acid resistance and the re-peeling resistance tend to be reduced, and the impact resistance is rather enhanced.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (13)

1. The oil and acid resistant foam cotton is characterized in that: the oleic acid resistant foam comprises a high-crosslinking-degree foam core material, a low-crosslinking-degree foam core material and a bonding layer, the high-crosslinking-degree foam core material is used as the center of the oleic acid resistant foam, the low-crosslinking-degree foam core materials on two sides are symmetrically arranged, and the high-crosslinking-degree foam core material and the low-crosslinking-degree foam core material are bonded through the bonding layer.
2. The oil and acid resistant foam cotton of claim 1, wherein: the materials required by the high crosslinking degree foam core material comprise, by weight: 100 parts of epichlorohydrin rubber, 0.3-2 parts of cross-linking agent A, 0.3-1.5 parts of cross-linking agent B, 0.2-2 parts of microsphere filler, 0.5-2 parts of aging agent, 0.1-1 part of light stabilizer, 0.5-2 parts of pigment and 350 parts of solvent 250-.
3. The oil and acid resistant foam cotton of claim 1, wherein: the materials required by the low-crosslinking-degree foam core material comprise, by weight: 100 parts of ternary chlorinated polyether elastomer, 10-20 parts of acrylate block copolymer, 10-30 parts of long-chain alkyl monomer, 0.5-3 parts of functional monomer, 0.1-0.5 part of thermal initiator, 1-2 parts of antioxidant, 0.2-2 parts of microsphere filler, 0.5-2 parts of pigment, 0.5-1.5 parts of curing agent and 600 parts of solvent.
4. The oil and acid resistant foam cotton of claim 2, wherein: the high crosslinking degree foam core material and the low crosslinking degree foam core material microsphere filler are one or more of hollow glass microspheres, pearl expanded rock, expanded acrylonitrile polymer microspheres and non-expanded acrylonitrile polymer microspheres, the solvent is one or more of toluene, xylene, tetrahydrofuran, cyclohexanone and acetone, and the pigment is one or more of alkaline black slurry, white slurry and colored slurry.
5. The oil and acid resistant foam cotton of claim 2, wherein: the epichlorohydrin rubber is one or more of epichlorohydrin homopolymerized rubber elastomer, binary epichlorohydrin, epichlorohydrin copolymerized rubber elastomer and ternary epichlorohydrin elastomer.
6. The oil and acid resistant foam cotton of claim 2, wherein: the light stabilizer is one or more of o-hydroxybenzophenone, benzotriazole, salicylate, triazine, substituted acrylonitrile and hindered amine, the crosslinking agent A is an amine crosslinking agent and comprises one or more of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, m-phenylenediamine, diaminodiphenylmethane, benzidine and bilateral amino ether, the crosslinking agent B is one or more of hydrogen peroxide, tert-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, azodiisobutyronitrile, azodiisovaleronitrile, azodiisoheptanonitrile, dimethyl azodiisobutyrate and azodicyclohexyl carbonitrile, and the aging agent is octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxy phenylpropionate, tris (2, 4-di-tert-butylphenyl) phosphite.
7. The oil and acid resistant foam cotton of claim 3, wherein: the acrylate block copolymer is a methyl methacrylate-butyl acrylate-methyl methacrylate block copolymer.
8. The oil and acid resistant foam cotton of claim 3, wherein: the long-chain alkyl monomer is alkyl (meth) acrylate containing 4-10 carbon atoms, and comprises one or more of butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate and n-octyl (meth) acrylate.
9. The oil and acid resistant foam cotton of claim 3, wherein: the functional monomer is one or more of (methyl) acrylic acid, itaconic acid, glycidyl (methyl) acrylate, hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate, (methyl) acrylamide and N-hydroxymethyl acrylamide.
10. The oil and acid resistant foam cotton of claim 3, wherein: the curing agent is one or more of isocyanate curing agent, epoxy curing agent and amine curing agent, the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, styrenated phenol, 2, 5-di-tert-butyl hydroquinone, 2' -dimethylene bis- (4-methyl-6-tert-butylphenol), 2, 4-trimethyl-1, 2-dihydroquinoline polymer, octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionate, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and 2-mercaptobenzimidazole.
11. The oil and acid foam resistant cotton of claim 3, wherein the thermal initiator is one or more of benzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile and azobisisoheptonitrile.
12. A preparation method of oleic acid-resistant foam is characterized by comprising the following steps: the method comprises the following steps:
s1: dissolving epichlorohydrin rubber by using a solvent, adding a microsphere filler, an aging agent, a light stabilizer, a pigment, a crosslinking agent A and a crosslinking agent B, uniformly mixing, removing bubbles, coating on a PET release liner 3, pre-drying at 40-100 ℃, removing the solvent, and baking at 160 ℃ for 5-10min to obtain a high-crosslinking-degree foam core material;
s2: dissolving a ternary chlorinated polyether elastomer and an acrylate block copolymer by using a solvent, heating to 80-90 ℃, introducing nitrogen while stirring to purge the liquid level for 60min, adding a long-chain alkyl monomer, a functional monomer and a thermal initiator, uniformly mixing, reacting for 4h, stopping introducing the nitrogen, adding an antioxidant, cooling, adding a microsphere filler, a pigment and a curing agent, uniformly mixing, removing bubbles, coating on a PET release substrate 3, pre-drying at 40-100 ℃, removing the solvent, and baking at 160 ℃ for 5-10min to obtain a low-crosslinking-degree foam core material;
s3: tearing off release films on two sides of the high-crosslinking-degree foam core material, respectively attaching adhesive layers on the two sides, and attaching the low-crosslinking-degree foam core material to the other side of each adhesive layer to obtain the oleic acid-resistant foam.
13. Use of the oil and acid resistant foam according to any one of claims 1 to 12, wherein: and tearing off the release films on the upper side and the lower side of the oil acid resistant foam, and attaching a glue surface layer to obtain the oil acid resistant foam adhesive tape.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5447992A (en) * 1994-06-13 1995-09-05 The Goodyear Tire & Rubber Company Heat and ozone resistant NBR/epichlorohydrin blends
JPH10140109A (en) * 1996-11-14 1998-05-26 Nitto Denko Corp Pressure-sensitive adhesive sheet or the like with foam support
JPH10204401A (en) * 1997-01-24 1998-08-04 Nippon Synthetic Chem Ind Co Ltd:The Pressure sensitive adhesive composition
JP2001003025A (en) * 1999-04-23 2001-01-09 Sekisui Chem Co Ltd Preparation of acrylic adhesive, and acrylic pressure- sensitive adhesive and sticky-processed product
CN104220544A (en) * 2012-04-04 2014-12-17 日东电工株式会社 Pressure-sensitive adhesive tape and tape roll
CN109880543A (en) * 2018-12-27 2019-06-14 新纶科技（常州）有限公司 A kind of foam substrate and double faced adhesive tape

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5447992A (en) * 1994-06-13 1995-09-05 The Goodyear Tire & Rubber Company Heat and ozone resistant NBR/epichlorohydrin blends
JPH10140109A (en) * 1996-11-14 1998-05-26 Nitto Denko Corp Pressure-sensitive adhesive sheet or the like with foam support
JPH10204401A (en) * 1997-01-24 1998-08-04 Nippon Synthetic Chem Ind Co Ltd:The Pressure sensitive adhesive composition
JP2001003025A (en) * 1999-04-23 2001-01-09 Sekisui Chem Co Ltd Preparation of acrylic adhesive, and acrylic pressure- sensitive adhesive and sticky-processed product
CN104220544A (en) * 2012-04-04 2014-12-17 日东电工株式会社 Pressure-sensitive adhesive tape and tape roll
CN109880543A (en) * 2018-12-27 2019-06-14 新纶科技（常州）有限公司 A kind of foam substrate and double faced adhesive tape

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