CN112280519B - Latent curing pressure-sensitive adhesive - Google Patents
Latent curing pressure-sensitive adhesive Download PDFInfo
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- CN112280519B CN112280519B CN202011261981.7A CN202011261981A CN112280519B CN 112280519 B CN112280519 B CN 112280519B CN 202011261981 A CN202011261981 A CN 202011261981A CN 112280519 B CN112280519 B CN 112280519B
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/40—Compositions for pressure-sensitive adhesives
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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)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to the field of pressure-sensitive adhesives, and particularly relates to a latent curing pressure-sensitive adhesive which comprises the following components in parts by mass: 10-45 parts of adipic acid polyester polyol, 20-41 parts of polyether polyol, 0.3 part of antioxidant, 0.15 part of wetting agent, 10-30 parts of polyacrylate, 4-10 parts of diisocyanate, 0.25 part of silane coupling agent, 0.1-1 part of catalyst and 10-25 parts of latent curing agent. The latent curing pressure-sensitive adhesive prepared by the invention can ensure that the polyurethane reaction type pressure-sensitive adhesive can be stably stored at room temperature, does not need sealing, is directly attached during use, can achieve higher peel strength and shear strength only by heating for 10-30min, and can be used at the external environment temperature in a wide range.
Description
Technical Field
The invention belongs to the field of pressure-sensitive adhesives, and particularly relates to a latent curing pressure-sensitive adhesive.
Background
The pressure-sensitive adhesive is used as a large variety of adhesives and is widely used in various fields, such as packaging, office, color printing, medical treatment, automotive interior and the like, common pressure-sensitive adhesives include solvent-based pressure-sensitive adhesives, emulsion-type pressure-sensitive adhesives and hot-melt pressure-sensitive adhesives, wherein the solvent-based pressure-sensitive adhesives are wide in applicability and good in adhesive property, but contain solvents and are harmful to human bodies and environment.
In recent years, the development of polyurethane hot melt adhesive is rapid in China, because the traditional oil-based adhesive or hot melt adhesive or solvent-containing adhesive or adhesive strength is poor, the polyurethane hot melt adhesive can eliminate the defects of the traditional oil-based adhesive or hot melt adhesive and the solvent-containing adhesive, the polyurethane reaction type pressure-sensitive adhesive has higher bonding strength and better high and low temperature resistance as a special pressure-sensitive adhesive compared with emulsion type and hot melt type pressure-sensitive adhesives, but the polyurethane reaction type pressure-sensitive adhesive also has the same defect as a polyurethane hot melt adhesive, namely polyurethane reaction type glue, the highest strength is achieved by the reaction of isocyanate groups in the glue and active hydrogen or water molecules, therefore, the polyurethane reaction type adhesive can not have water vapor in the packaging and storing process, namely, the polyurethane reaction type adhesive needs to be completely sealed and stored, otherwise, the polyurethane adhesive can be invalid, and the polyurethane reaction type pressure-sensitive adhesive is particularly suitable for the packaging and the storage, so that the packaging and the storage are very inconvenient.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a latent curing pressure-sensitive adhesive, which solves the problem of poor practicability of the existing pressure-sensitive adhesive, improves the stability of the pressure-sensitive adhesive by utilizing a latent curing agent, and meets the requirement of unnecessary sealing at normal temperature.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
the latent curing pressure-sensitive adhesive comprises the following components in parts by mass: 10-45 parts of adipic acid polyester polyol, 20-41 parts of polyether polyol, 0.3 part of antioxidant, 0.15 part of wetting agent, 10-30 parts of polyacrylate, 4-10 parts of diisocyanate, 0.25 part of silane coupling agent, 0.01-1 part of catalyst and 10-25 parts of latent curing agent.
Wherein the adipic acid polyester polyol adopts one or more of a poly adipic acid-ethylene glycol ester copolymer, a poly adipic acid-diethylene glycol ester copolymer, an adipic acid-1, 4-butanediol copolymer, an adipic acid-1, 6-hexanediol copolymer, an adipic acid-neopentyl glycol copolymer and adipic acid-cyclohexanedimethanol.
The adipic acid polyester polyol is a copolymer of hexanediol and two or more than two micromolecular diols.
The molecular weight of the adipic acid polyester polyol is 1000-3500.
The polyether glycol comprises general polypropylene glycol with the molecular weight of 1000-5000, and the general polypropylene glycol adopts difunctional polypropylene glycol or multifunctional polypropylene glycol.
The antioxidant adopts Irgano 1010 of Basfu, the wetting agent adopts MFP200 of Qingdaolin Co Ltd, the silane coupling agent adopts Hangzhou boiling point KH560, and the catalyst adopts Detony DY-150.
The polyacrylate is one of BM751, BM723 and BM342 of Brilliant chemical engineering company or other acrylic resin with hydroxyl.
The diisocyanate is one or more of isophorone diisocyanate (IPDI), HDI, H12MDI and MDI.
The latent curing agent is prepared by carrying out addition reaction on polyester, polyether or a polyester-polyether mixture and diisocyanate or polyisocyanate and then blocking the mixture with micromolecules, the blocked prepolymer is relatively stable at normal temperature, but under the condition of raising the temperature, the blocked product starts to be deblocked, and the deblocking temperature depends on the type of the diisocyanate and the micromolecule blocking agent. The strength of chemical bonds formed by isocyanate in the prepolymers of different blocking agents determines the deblocking temperature. Commonly used deblocking agents are, for example, methanol, phenol, N-valent aniline, acetoxime, epsilon-caprolactam, acetylacetone and the like. At this time, NCO group in prepolymer is released to react with active (OH, NH) in system 2 SH, etc.) undergoes rapid crosslinking curing. The latent curing agent adopts one of 9200-150C, 9300-110C and XB-G282; or other latent curing agents that have an unblocking temperature.
The preparation method of the latent curing pressure-sensitive adhesive comprises the following steps:
step 1, weighing raw materials according to a proportion;
step 2, adding adipic acid polyester polyol, polyether polyol, an antioxidant and a wetting agent into a reaction kettle, uniformly stirring, and heating to 120 ℃; adding polyacrylate in the stirring process, heating to 140 ℃, accelerating the stirring for 1h, and then dehydrating for 1h under negative vacuum of-0.1 MPa;
step 3, cooling the reaction kettle to 115-plus-120 ℃, adding diisocyanate, and reacting for 2h at 125-plus-130 ℃ under the protection of nitrogen;
step 4, adding a catalyst, and stirring for reacting for 15 min;
step 5, adding a latent curing agent and a silane coupling agent, and stirring to react for 15 min;
and 6, defoaming for 15min, discharging, and placing in an aluminum foil bag or other containers.
From the above description, it can be seen that the present invention has the following advantages:
the latent curing pressure-sensitive adhesive prepared by the invention can ensure that the polyurethane reaction type pressure-sensitive adhesive can be stably stored at room temperature, does not need sealing, is directly attached during use, can achieve higher peel strength and shear strength only by heating for 10-30min, and can be used at a wide external environment temperature.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
A latent curing pressure-sensitive adhesive is prepared by the following steps:
step 1, weighing raw materials: 20.7g of poly (ethylene adipate-glycol) copolymer (molecular weight is 1000), 40.7g of polyether polyol (trademark PPG2000), 0.3g of antioxidant (trademark Irgano 1010), 0.15g of wetting agent (trademark MFP200), 21.02g of polyacrylic resin (trademark BM723, 5g of BM 751), 7.03g of diisocyanate (trademark IPDI), 0.1g of catalyst (trademark DY-150) and 10g of latent curing agent (trademark 9200-150C);
step 2, adding the poly adipic acid-glycol ester copolymer, polyether polyol, an antioxidant and a wetting agent into a reaction kettle, uniformly stirring and heating to 120 ℃, then adding polyacrylate, heating to 140 ℃, accelerating stirring for 1h, and dehydrating for 1h under the vacuum degree of-0.1 MPa;
step 3, cooling the reaction kettle to 115 ℃, adding IPDI, and reacting for 2 hours at 125 ℃ under the protection of nitrogen;
step 4, adding a catalyst, and stirring for reacting for 15 min;
step 5, adding a latent curing agent and a silane coupling agent, and stirring to react for 15 min;
and 6, defoaming for 15min, discharging, and placing in an aluminum foil bag.
Step 2
A latent curing pressure-sensitive adhesive is prepared by the following steps:
step 1, weighing raw materials: 35g of poly adipic acid-1, 6-hexanediol copolymer (molecular weight 1000 accounts for 14.3g, molecular weight 2000 accounts for 20.7g), 29.1g of polyether polyol (trade name PPG2000), 0.3g of antioxidant (trade name Irgano 1010), 0.15g of wetting agent (trade name MFP200), 14.6g of polyacrylic resin (trade name BM723 accounts for 11.1g, BM751 accounts for 3.5g), 5.1g of diisocyanate (trade name IPDI), 0.1g of catalyst (trade name DY-150), and 17.2g of latent curing agent (trade name 9200-150C);
step 2, adding the poly adipic acid-1, 6-hexanediol copolymer, polyether polyol, an antioxidant and a wetting agent into a reaction kettle, uniformly stirring, heating to 120 ℃, then adding polyacrylate, heating to 140 ℃, accelerating stirring for 1h, and dehydrating for 1h under the vacuum degree of-0.1 MPa;
step 3, cooling the reaction kettle to 120 ℃, adding IPDI, and reacting for 2 hours at 130 ℃ under the protection of nitrogen;
step 4, adding a catalyst, and stirring for reacting for 15 min;
step 5, adding a latent curing agent and a silane coupling agent, and stirring to react for 15 min;
and 6, defoaming for 15min, discharging, and placing in an aluminum foil bag.
Example 3
A latent curing pressure-sensitive adhesive is prepared by the following steps:
step 1, weighing raw materials: 42.27G (molecular weight 2000) of adipic acid-1, 4 butanediol copolymer, 21.46G of polyether polyol (trademark PPG2000), 0.3G of antioxidant (trademark Irgano 1010), 0.15G of wetting agent (trademark MFP200), 10.73G of polyacrylic resin (trademark BM342), 4.38G of diisocyanate (trademark IPDI), 1G of catalyst (trademark DY-150), 19.33G of latent curing agent (trademark XB-G282) and 0.25G of silane coupling agent (trademark KH 560);
step 2, adding the adipic acid-1, 4-butanediol copolymer, polyether polyol, an antioxidant and a wetting agent into a reaction kettle, uniformly stirring, heating to 120 ℃, then adding polyacrylate, heating to 140 ℃, accelerating stirring for 1h, and dehydrating for 1h under the vacuum degree of-0.1 MPa;
step 3, cooling the reaction kettle to 118 ℃, adding IPDI, and reacting for 2 hours at 128 ℃ under the protection of nitrogen;
step 4, adding a catalyst, and stirring for reacting for 15 min;
step 5, adding a latent curing agent and a silane coupling agent, and stirring to react for 15 min;
and 6, defoaming for 15min, discharging, and placing in an aluminum foil bag.
Example 4
A latent curing pressure-sensitive adhesive is prepared by the following steps:
step 1, weighing raw materials: 45.18g (molecular weight 2000) of a poly adipic acid-1, 6-hexanediol copolymer, 22.94g of polyether polyol (trademark PPG2000), 0.3g of an antioxidant (trademark Irgano 1010), 0.15g of a wetting agent (trademark MFP200), 11.47g of a polyacrylic resin (trademark BM342), 4.68g of diisocyanate (trademark IPDI), 1g of a catalyst (trademark DY-150), 13.78g of a latent curing agent (trademark 9300 ion 110C) and 0.25g of a silane coupling agent (trademark KH 560);
step 2, adding the poly adipic acid-1, 6-hexanediol copolymer, polyether polyol, an antioxidant and a wetting agent into a reaction kettle, uniformly stirring and heating to 120 ℃, then adding polyacrylate, heating to 140 ℃, accelerating stirring for 1h, and dehydrating for 1h under the vacuum degree of-0.1 MPa;
step 3, cooling the reaction kettle to 118 ℃, adding IPDI, and reacting for 2 hours at 128 ℃ under the protection of nitrogen;
step 4, adding a catalyst, and stirring for reacting for 15 min;
step 5, adding a latent curing agent and a silane coupling agent, and stirring to react for 15 min;
and 6, defoaming for 15min, discharging, and placing in an aluminum foil bag.
The pressure-sensitive adhesive of the embodiment 1 to the embodiment 4 is applied to the fan blade, and the attaching part is the polyurethane elastomer and is attached to the inner plate of the fan.
The competitive product pressure-sensitive adhesive and the polyurethane reactive pressure-sensitive adhesive are taken as comparative examples
The pressure of examples 1 to 4 was compared with the pressure-sensitive adhesives of the competitive products and the polyurethane reactive pressure-sensitive adhesive as follows:
as can be seen from the table above, the final bonding strength of the latent curing pressure-sensitive adhesive prepared by the invention is 2-4 times of that of a competitive product, and the latent curing pressure-sensitive adhesive can be stored without sealing compared with a polyurethane reactive pressure-sensitive adhesive, so that the limitation that the packaging of the polyurethane reactive pressure-sensitive adhesive needs strict sealing and storage is removed.
In order to prepare the pressure-sensitive adhesive with higher pressure-sensitive characteristic before curing, polyfunctional polyether and polyfunctional polyester or polyhydroxy acrylic resin are used to ensure that more prepolymers with three-dimensional structures are formed after isocyanate reaction. The prepolymer which is blocked by hydroxyl and contains a three-dimensional structure is used together with a latent curing agent, and the dosage of the latent curing agent is selected according to the hydroxyl value and the content of isocyanic acid radical of the latent curing agent. The softness and hardness of the colloid are determined by the structure of the polyol and the acrylic acid. Therefore, after the trifunctional polyether or polyester, the acrylic resin and the blocked latent isocyanate curing agent are used together, the peel strength can reach 1.0MPa without losing the pressure-sensitive characteristic of the product and the high and low temperature resistance characteristic after curing. The shear strength of the common acrylic pressure-sensitive adhesive is only 0.13 MPa.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; and are within the scope of the present invention as long as the requirements of use are met.
Claims (8)
1. A latent curing pressure-sensitive adhesive is characterized in that: the mass ratio is as follows: 10-45 parts of adipic acid polyester polyol, 20-41 parts of polyether polyol, 0.3 part of antioxidant, 0.15 part of wetting agent, 10-30 parts of polyacrylate, 4-10 parts of diisocyanate, 0.25 part of silane coupling agent, 0.01-1 part of catalyst and 10-25 parts of latent curing agent;
the polyacrylate adopts acrylic resin with hydroxyl;
the latent curing agent is prepared by carrying out addition reaction on polyester, polyether or a polyester-polyether mixture and diisocyanate or polyisocyanate and then blocking the reaction product by micromolecules.
2. The latent curable pressure sensitive adhesive of claim 1, wherein: the adipic acid polyester polyol is one or more of a poly adipic acid-ethylene glycol ester copolymer, a poly adipic acid-diethylene glycol ester copolymer, an adipic acid-1, 4-butanediol copolymer, an adipic acid-1, 6-hexanediol copolymer, an adipic acid-neopentyl glycol copolymer and adipic acid-cyclohexanedimethanol.
3. A latent curing pressure-sensitive adhesive according to claim 1, wherein: the adipic acid polyester polyol is a copolymer of hexanediol and two or more than two micromolecular diols.
4. The latent curable pressure sensitive adhesive of claim 1, wherein: the molecular weight of the adipic acid polyester polyol is 1000-3500.
5. The latent curable pressure sensitive adhesive of claim 1, wherein: the polyether polyol comprises general-purpose polypropylene glycol with the molecular weight of 1000-5000.
6. The latent curable pressure sensitive adhesive of claim 1, wherein: the antioxidant adopts Irgano 1010 of Basfu, the wetting agent adopts MFP200 of Qingdaolin Co Ltd, the silane coupling agent adopts Hangzhou boiling point KH560, and the catalyst adopts Detony DY-150.
7. The latent curable pressure sensitive adhesive of claim 1, wherein: the diisocyanate is one or more of isophorone diisocyanate (IPDI), HDI, H12MDI and MDI.
8. The latent curable pressure sensitive adhesive of claim 1, wherein: the preparation method of the latent curing pressure-sensitive adhesive comprises the following steps:
step 1, weighing raw materials according to a proportion;
step 2, adding adipic acid polyester polyol, polyether polyol, an antioxidant and a wetting agent into a reaction kettle, uniformly stirring, and heating to 120 ℃; adding polyacrylate in the stirring process, heating to 140 ℃, accelerating the stirring for 1h, and then dehydrating for 1h under negative vacuum of-0.1 MPa;
step 3, cooling the reaction kettle to 115-plus-120 ℃, adding diisocyanate, and reacting for 2h at 125-plus-130 ℃ under the protection of nitrogen;
step 4, adding a catalyst, and stirring for reacting for 15 min;
step 5, adding a latent curing agent and a silane coupling agent, and stirring to react for 15 min;
and 6, defoaming for 15min, discharging, and placing in an aluminum foil bag or other containers.
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| CN202011261981.7A CN112280519B (en) | 2020-11-12 | 2020-11-12 | Latent curing pressure-sensitive adhesive |
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| CN202011261981.7A CN112280519B (en) | 2020-11-12 | 2020-11-12 | Latent curing pressure-sensitive adhesive |
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| CN112280519B true CN112280519B (en) | 2022-09-20 |
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| CN116144313A (en) * | 2023-01-04 | 2023-05-23 | 湖北回天新材料股份有限公司 | Single-component polyurethane low-temperature thermal-curing structural adhesive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627362A (en) * | 2013-11-29 | 2014-03-12 | 烟台德邦科技有限公司 | Reactive polyurethane hot melt adhesive and preparation method thereof |
| CN107987778A (en) * | 2017-12-08 | 2018-05-04 | 杭州之江有机硅化工有限公司 | A kind of household electrical appliances reaction type polyurethane hot-melt adhesive and preparation method thereof |
| CN108753167A (en) * | 2018-05-15 | 2018-11-06 | 广东生益科技股份有限公司 | A kind of resin combination, the stack bus bar insulated rubber film and preparation method thereof comprising it |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627362A (en) * | 2013-11-29 | 2014-03-12 | 烟台德邦科技有限公司 | Reactive polyurethane hot melt adhesive and preparation method thereof |
| CN107987778A (en) * | 2017-12-08 | 2018-05-04 | 杭州之江有机硅化工有限公司 | A kind of household electrical appliances reaction type polyurethane hot-melt adhesive and preparation method thereof |
| CN108753167A (en) * | 2018-05-15 | 2018-11-06 | 广东生益科技股份有限公司 | A kind of resin combination, the stack bus bar insulated rubber film and preparation method thereof comprising it |
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