CN112708377A - Adhesive for bonding polyolefin low-surface-energy material - Google Patents
Adhesive for bonding polyolefin low-surface-energy material Download PDFInfo
- Publication number
- CN112708377A CN112708377A CN202011561421.3A CN202011561421A CN112708377A CN 112708377 A CN112708377 A CN 112708377A CN 202011561421 A CN202011561421 A CN 202011561421A CN 112708377 A CN112708377 A CN 112708377A
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- CN
- China
- Prior art keywords
- parts
- adhesive
- modified rosin
- rosin resin
- epoxy resin
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Classifications
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- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The adhesive for bonding the polyolefin low-surface-energy material comprises the following components in parts by weight: acrylic copolymer, polyhydroxy olefin oligomer, modified rosin resin, polyisocyanate curing agent and polyfunctional epoxy resin crosslinking agent. Specifically, the paint comprises the following components in parts by weight: 65-85 parts of acrylic copolymer, 5-10 parts of polyhydroxyolefin oligomer, 10-25 parts of modified rosin resin, 3-5 parts of polyisocyanate curing agent and 0.01-0.02 part of polyfunctional epoxy resin crosslinking agent. The adhesive of the invention can be used for bonding polyolefin low surface energy substances such as polyethylene, polypropylene and the like, can obtain ideal bonding strength, and is moisture-proof and heat-resistant.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to an adhesive for bonding a polyolefin low-surface-energy material.
Background
Surface energy is a measure of the breakdown of chemical bonds between molecules when creating a surface of a substance. In solid physics, surface atoms have more energy than atoms inside a substance, and therefore, according to the principle of energy minimization, atoms tend spontaneously to the inside of a substance rather than to the surface.
The low surface energy materials such as polyethylene, polypropylene and other polyolefins are widely applied in daily life and industry, common adhesives are difficult to bond, common pressure-sensitive adhesives are difficult to wet the surface to form firm bonding, and therefore, the adhesives which can be used for bonding the surfaces of the polyethylene, polypropylene and other polyolefins are urgently needed to be provided.
Disclosure of Invention
The present invention is directed to the above-mentioned deficiencies of the prior art and provides an adhesive for bonding polyolefin low surface energy materials, which can be used for bonding polyolefin low surface energy materials such as polyethylene and polypropylene.
The specific technical scheme is as follows:
the adhesive for bonding the polyolefin low-surface-energy material comprises the following components in parts by weight: acrylic copolymer, polyhydroxy olefin oligomer, modified rosin resin, polyisocyanate curing agent and polyfunctional epoxy resin crosslinking agent.
Specifically, the paint comprises the following components in parts by weight: 65-85 parts of acrylic copolymer, 5-10 parts of polyhydroxyolefin oligomer, 10-25 parts of modified rosin resin, 3-5 parts of polyisocyanate curing agent and 0.01-0.02 part of polyfunctional epoxy resin crosslinking agent.
All the parts are solid content parts.
Wherein the acrylic copolymer can be obtained by synthesis according to Chinese patent CN201611029662 which we have previously applied.
The adhesive obtained by the invention can be used for bonding low surface energy polyolefin substances such as polyethylene, polypropylene and the like, and has good bonding effect.
Furthermore, the main chain of the polyhydroxy olefin oligomer is a saturated hydrocarbon skeleton, and the polyhydroxy olefin oligomer has a plurality of hydroxyl groups and has a molecular weight of 1000-3000. Examples of preferred polyhydroxyolefin oligomers include POLYTAIL produced by Mitsubishi chemical corporation.
Polyhydroxy olefin oligomer is added, and is cured by polyisocyanate, so that the polyhydroxy olefin oligomer and the acrylic copolymer can be crosslinked together, and the adhesive force of the adhesive to the surface of polyolefin is improved.
Further, the modified rosin resin can be selected from modified rosin resins with a softening point of 85-140 ℃ produced by Mitsukawa chemical corporation, preferably modified rosin resins with a softening point of 95-125 ℃, and can be selected from specially modified GB-100, GB-115, GB-125, D-125 and hydrogenated rosin resins GH-100.
The rosin resin has no adhesive force, but has better wetting effect on the surface of the material, and the initial adhesion and the bonding property of the adhesive can be improved by adding the rosin resin into the pressure-sensitive adhesive of an acrylic system. According to the invention, the acrylic pressure-sensitive adhesive is modified by using the special modified rosin resin or hydrogenated rosin resin as the tackifier, so that the initial viscosity is increased, and the wettability of the acrylic pressure-sensitive adhesive on low-surface-energy materials such as polyolefin is improved.
Further, the polyisocyanate curing agent is tolylene diisocyanate-trimethylolpropane (TDI-TMP) adduct, and a Desmodur L75 curing agent of Bayer is used.
Further, the multifunctional Epoxy resin cross-linking agent is a trifunctional or tetrafunctional Epoxy resin, preferably 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, 4- (2, 3-epoxypropoxy) -N, N-bis (2, 3-epoxypropyl) aniline, N, N, N, -tetracyclooxypropyl-4, 4-diaminodiphenylmethane, and optionally Syna Epoxy S-500, Syna Epoxy S-500m, Syna Epoxy S-510, Syna Epoxy S-610, Syna Epoxy S-720, and the like, produced by Naxi.
And a small amount of polyfunctional epoxy resin crosslinking agent is added, so that the crosslinking density of the system is improved, and the heat resistance and the permanent adhesion are improved.
The above adhesive can be prepared by the following method:
respectively dissolving modified rosin resin and polyhydroxy olefin oligomer in an organic solvent, then mixing the acrylic copolymer, the modified rosin resin solution and the polyhydroxy olefin oligomer solution at normal temperature, stirring for 0.5h, then adding the polyisocyanate curing agent and the polyfunctional epoxy resin crosslinking agent while stirring, and stirring for 0.5h to obtain the adhesive composition.
The invention has the following beneficial effects:
the adhesive of the present invention can be used for bonding polyolefin low surface energy substances such as polyethylene, polypropylene, etc., can obtain ideal bonding strength, and is moisture-proof and heat-resistant.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
An adhesive was prepared, and a double-sided non-woven tape sample was prepared using the adhesive.
The components of the adhesive are as follows: the polyhydroxyolefin oligomer is POLYTAIL H (molecular weight 2700, hydroxyl value 45-50 mg KOH/g) produced by Mitsubishi chemical corporation; the modified rosin resin is rosin resin GB-100 (softening point 95-105 ℃, acid value less than 10) produced by Mitsukawa; the polyisocyanate curing agent is a Desmodur L75 curing agent produced by Bayer company; the polyfunctional Epoxy resin cross-linking agent is Syna Epoxy S-500[4- (2, 3-epoxypropoxy) -N, N-di (2, 3-epoxypropyl) aniline ] produced by Xinnaxi.
The preparation method comprises the following steps:
(1) acrylic copolymer Synthesis: acrylic copolymer S1 (45% solids content) was synthesized with reference to Chinese patent CN 201611029662;
(2) dissolving the modified rosin resin: dissolving the mixture into resin solution S2 with the solid content of 50 percent by using ethyl acetate, wherein the dissolving temperature is normal temperature, and the dissolving time is 0.5 h;
(3) polyhydroxyolefin oligomer dissolution: dissolving the mixture into a solution S3 with the solid content of 20% by using toluene, wherein the dissolving temperature is 70-80 ℃, and the dissolving time is 2 hours;
(4) preparation of adhesive composition: 166g of synthetic acrylic copolymer S1 (solid content: 45%), 30g of modified rosin resin solution S2 and 50g of polyhydroxyolefin oligomer solution S3 were weighed, stirred at normal temperature for 0.5 hour, and then stirred while adding 4.78g of polyisocyanate curing agent and 0.015g of polyfunctional epoxy resin crosslinking agent, and stirred for 0.5 hour to obtain an adhesive composition with a solid content of 41.4%;
(5) adhesive composition coating tape samples: a wire bar for the adhesive composition obtained in the step (4)Coating the release surface of the single-sided release film by a coater, baking in an oven at 80-110 deg.C for 3-5 min to obtain a dry adhesive with a thickness of 70 μm, and compounding to 14g/m at 100 deg.C and 0.6MPa2And compounding the dried adhesive agent on the two surfaces of the non-woven fabric substrate to obtain a double-sided non-woven fabric adhesive tape sample with the thickness of 150-160 mu m.
Example 2
Referring to example 1, the difference from example 1 is that: the modified rosin resin and the like were replaced with GB-125 (hydrogenated rosin resin) produced by Mitsukawa chemical Co., Ltd.
The remaining technical features are the same as those of example 1.
Example 3
Referring to example 1, the difference from example 1 is that: the same mass of polyhydroxyolefin oligomer was replaced with POLYTAIL HA (molecular weight 2000) produced by Mitsubishi chemical corporation.
The remaining technical features are the same as those of example 1.
Example 4
Referring to example 1, the difference from example 1 is that: the quality of a polyfunctional Epoxy resin cross-linking agent and the like is replaced by Syna Epoxy S-610[1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane ] produced by Xinnaxi.
The remaining technical features are the same as those of example 1.
Comparative example 1
Referring to example 1, the difference from example 1 is that: no polyhydroxyolefin oligomer was added.
The remaining technical features are the same as those of example 1.
Comparative example 2
Referring to example 1, the difference from example 1 is that: no modified rosin resin was added.
The remaining technical features are the same as those of example 1.
Experiment of
The adhesive strength of the double-sided nonwoven tape samples obtained in examples 1 to 4 and comparative examples 1 to 2 was evaluated by the following test method:
(1) the peel strength test of the double-sided non-woven fabric adhesive tape sample is carried out according to the method described in the national standard GB/T2792-2014, and the adhesive force to the standard steel plate and the PP plate is respectively tested;
(2) carrying out a permanent adhesion test on a double-sided non-woven fabric tape sample according to the method described in the national standard GB/T4851-2014;
(3) peel strength test after humid heat aging: and respectively attaching the double-sided non-woven fabric adhesive tape samples to a steel plate and an untreated PP plate to prepare test samples, and after 1000 hours under the condition of 60 ℃ and 90% RH humid heat aging, carrying out peel strength test according to the method of the national standard GB/T2792-2014.
The results are shown in Table 1.
Table 1: data for testing performance of the double-sided non-woven fabric tapes obtained in examples 1 to 4 and comparative examples 1 to 2
As can be seen from the results shown in table 1, the adhesive provided by the present invention has good adhesion to low surface energy materials such as polyolefins, high permanent adhesion, excellent resistance to wet heat aging, and industrial applicability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The adhesive for bonding the polyolefin low-surface-energy material is characterized by comprising the following components in parts by weight: acrylic copolymer, polyhydroxy olefin oligomer, modified rosin resin, polyisocyanate curing agent and polyfunctional epoxy resin crosslinking agent.
2. The adhesive according to claim 1, which comprises the following components in parts by weight: 65-85 parts of acrylic copolymer, 5-10 parts of polyhydroxyolefin oligomer, 10-25 parts of modified rosin resin, 3-5 parts of polyisocyanate curing agent and 0.01-0.02 part of polyfunctional epoxy resin crosslinking agent.
3. The adhesive according to claim 1 or 2, wherein the polyhydroxyolefin oligomer has a saturated hydrocarbon skeleton in its main chain, has a plurality of hydroxyl groups, and has a molecular weight of 1000 to 3000.
4. The adhesive according to claim 1 or 2, wherein the modified rosin resin is a modified rosin resin or a modified hydrogenated rosin resin having a softening point of 85 to 140 ℃.
5. The adhesive according to claim 4, wherein the modified rosin resin has a softening point of 95 to 125 ℃.
6. Adhesive according to claim 1 or 2, characterized in that the polyisocyanate crosslinking agent is an adduct of toluene diisocyanate-trimethylolpropane.
7. Adhesive according to claim 1 or 2, characterized in that the multifunctional epoxy resin cross-linker is a trifunctional or tetrafunctional epoxy resin.
8. The adhesive of claim 7 wherein the multifunctional epoxy resin crosslinking agent is one of 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 4- (2, 3-epoxypropoxy) -N, N-bis (2, 3-epoxypropyl) aniline, N, N, N, -tetracyclooxypropyl-4, 4-diaminodiphenylmethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011561421.3A CN112708377A (en) | 2020-12-25 | 2020-12-25 | Adhesive for bonding polyolefin low-surface-energy material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011561421.3A CN112708377A (en) | 2020-12-25 | 2020-12-25 | Adhesive for bonding polyolefin low-surface-energy material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112708377A true CN112708377A (en) | 2021-04-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011561421.3A Pending CN112708377A (en) | 2020-12-25 | 2020-12-25 | Adhesive for bonding polyolefin low-surface-energy material |
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| Country | Link |
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| CN (1) | CN112708377A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003277716A (en) * | 2002-03-27 | 2003-10-02 | Sekisui Chem Co Ltd | Moisture-curable adhesive composition |
| CN1735672A (en) * | 2002-11-06 | 2006-02-15 | 东亚合成株式会社 | Adhesive composition and method of bonding |
| JP2017019961A (en) * | 2015-07-14 | 2017-01-26 | オート化学工業株式会社 | Adhesive composition |
| CN106589434A (en) * | 2016-11-15 | 2017-04-26 | 烟台德邦科技有限公司 | Solar double-glass photovoltaic module laminating and edge sealing adhesive tape and preparation method thereof |
| CN106753177A (en) * | 2016-12-26 | 2017-05-31 | 天津博苑高新材料有限公司 | The adhesive and preparation method of effectively bonding can be realized to card stock at low temperature |
| CN106928868A (en) * | 2017-03-30 | 2017-07-07 | 苏州凡赛特材料科技有限公司 | A kind of pressure-sensitive adhesive agent and preparation method thereof |
| CN107922809A (en) * | 2015-09-01 | 2018-04-17 | 琳得科株式会社 | Adhesive composition and bonding sheet |
| CN109321197A (en) * | 2018-10-11 | 2019-02-12 | 刘凤语 | Bi-component optical cable filling with sealant and its preparation method and application, optical cable |
| CN110746908A (en) * | 2019-09-17 | 2020-02-04 | 深圳市百泉河实业有限公司 | Dual-curing adhesive composition containing modified polyolefin |
-
2020
- 2020-12-25 CN CN202011561421.3A patent/CN112708377A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003277716A (en) * | 2002-03-27 | 2003-10-02 | Sekisui Chem Co Ltd | Moisture-curable adhesive composition |
| CN1735672A (en) * | 2002-11-06 | 2006-02-15 | 东亚合成株式会社 | Adhesive composition and method of bonding |
| JP2017019961A (en) * | 2015-07-14 | 2017-01-26 | オート化学工業株式会社 | Adhesive composition |
| CN107922809A (en) * | 2015-09-01 | 2018-04-17 | 琳得科株式会社 | Adhesive composition and bonding sheet |
| CN106589434A (en) * | 2016-11-15 | 2017-04-26 | 烟台德邦科技有限公司 | Solar double-glass photovoltaic module laminating and edge sealing adhesive tape and preparation method thereof |
| CN106753177A (en) * | 2016-12-26 | 2017-05-31 | 天津博苑高新材料有限公司 | The adhesive and preparation method of effectively bonding can be realized to card stock at low temperature |
| CN106928868A (en) * | 2017-03-30 | 2017-07-07 | 苏州凡赛特材料科技有限公司 | A kind of pressure-sensitive adhesive agent and preparation method thereof |
| CN109321197A (en) * | 2018-10-11 | 2019-02-12 | 刘凤语 | Bi-component optical cable filling with sealant and its preparation method and application, optical cable |
| CN110746908A (en) * | 2019-09-17 | 2020-02-04 | 深圳市百泉河实业有限公司 | Dual-curing adhesive composition containing modified polyolefin |
Non-Patent Citations (1)
| Title |
|---|
| 李子东 等 编著: "《胶黏剂助剂》", 30 June 2009, 北京：化学工业出版社 * |
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Application publication date: 20210427 |
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