CN112592679B - Water-based PVC (polyvinyl chloride) laminated adhesive for paint-free door and preparation process thereof - Google Patents
Water-based PVC (polyvinyl chloride) laminated adhesive for paint-free door and preparation process thereof Download PDFInfo
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- 239000000853 adhesive Substances 0.000 title claims abstract description 93
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000915 polyvinyl chloride Polymers 0.000 title description 32
- 239000004800 polyvinyl chloride Substances 0.000 title description 32
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 37
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 37
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 35
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 33
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 33
- 239000000839 emulsion Substances 0.000 claims abstract description 33
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 33
- -1 aldehyde ketone Chemical class 0.000 claims abstract description 29
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 28
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 28
- 239000011976 maleic acid Substances 0.000 claims abstract description 28
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 28
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000000084 colloidal system Substances 0.000 claims abstract description 13
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 4
- 239000012939 laminating adhesive Substances 0.000 abstract description 16
- 239000005038 ethylene vinyl acetate Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000243 solution Substances 0.000 description 17
- 239000003292 glue Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000002023 wood Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000007666 vacuum forming Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000006172 buffering agent Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001069 triethyl citrate Substances 0.000 description 3
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 3
- 235000013769 triethyl citrate Nutrition 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical group [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- 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
- C09J131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
-
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
The application relates to the field of adhesives, and particularly discloses a water-based PVC laminated adhesive for a paint-free door and a preparation process thereof, wherein the adhesive comprises the following raw materials: 30-35 parts of water; 95-100 parts of EVA emulsion; 25-30 parts of maleic acid modified rosin resin; 12-15 parts of water-based aldehyde ketone resin; 0.5-1 part of hydroxyethyl cellulose; 70-80 parts of aqueous polyurethane dispersion. The process comprises the following steps: s1: mixing hydroxyethyl cellulose with water according to the proportion of 1:5 to obtain a hydroxyethyl cellulose colloid; s2: mixing the rest water with the EVA emulsion, heating to 75-80 ℃, and adding the aqueous polyurethane dispersion to obtain a first mixture; s3: heating the first mixture to 110-115 ℃, adding and mixing hydroxyethyl cellulose colloid, diethyl phthalate and sodium dodecyl benzene sulfonate to obtain a second mixture; s4: and respectively heating the second mixture and the maleic acid modified rosin resin to 170-175 ℃, uniformly mixing, adding the water-based aldehyde ketone resin into the mixture, mixing, and cooling to obtain a finished product. The laminating adhesive prepared by the application has better adhesive strength.
Description
Technical Field
The application relates to the technical field of adhesives, in particular to a water-based PVC laminated adhesive for a paint-free door and a preparation process thereof.
Background
The paint-free door is a wooden door without painting as the name implies, and most of the paint-free doors on the market refer to PVC faced doors which are formed by processing the outermost surface of a solid wood composite door or a mould pressing door by PVC vacuum forming. When PVC is bonded with the door panel, the film-coated adhesive is needed.
The prior coating adhesive is generally a solvent type coating adhesive, has the advantages of high bonding fastness, quick drying, good brightness, no foaming and the like, but easily volatilizes toxic gas in the using process and easily causes environmental pollution. Therefore, in recent years, water-based coated adhesives are becoming the mainstream of the market, and the water-based coated adhesives take water as a solvent, can avoid the generation of toxic volatile gases, and are more environment-friendly and safer.
The furniture laminating adhesive disclosed in the Chinese patent application with the application number of CN201710732835.X is prepared from the following components in parts by weight: 40-50 parts of triethyl citrate, 2-10 parts of acrylate compounds, 10-15 parts of functional auxiliary agents, 0.1-0.3 part of buffering agents, 2-10 parts of emulsifying agents, 0.5-4 parts of initiating agents, 15-30 parts of deionized water, 0.1-1.5 parts of oxidizing agents and 0.1-1.5 parts of reducing agents. Can be used for PVC film of furniture.
Because the solvent of the water-based laminating adhesive is water, the problem of low bonding strength commonly exists in the existing water-based laminating adhesive under the limitation of solubility of water and organic components.
Disclosure of Invention
In order to improve the adhesive strength of the water-based PVC laminated adhesive, the application provides the water-based PVC laminated adhesive for the paint-free door and the preparation process thereof.
In a first aspect, the application provides a water-based type PVC laminated adhesive for paint-free door, which adopts the following technical scheme:
a water-based PVC laminated adhesive for a paint-free door is mainly prepared from the following raw materials in parts by mass:
30-35 parts of water;
95-100 parts of EVA emulsion;
25-30 parts of maleic acid modified rosin resin;
12-15 parts of water-based aldehyde ketone resin;
0.5-1 part of hydroxyethyl cellulose;
70-80 parts of aqueous polyurethane dispersion.
By adopting the technical scheme, water is used as a solvent, and EVA emulsion and water-based polyurethane are used as base materials, so that a main adhesive source is provided for the film-coated adhesive. And the maleic acid modified rosin resin and the water-based aldehyde ketone resin are added in the system, and the two components can form good hydrogen bonds with water, so that the two components have certain solubility in the water and can also form hydrogen bonds with the EVA emulsion to achieve good combination. The rosin resin has good glossiness, heat resistance and adhesiveness, and the matching capacity of the rosin resin and a water-based glue solution is improved and the overall bonding strength is improved after the rosin resin is modified by maleic anhydride.
The hydroxyethyl cellulose is also added into the raw materials, has good thickening and moisture protection effects, and can keep good fluidity of the system after a large amount of organic components are added. And the cellulose can also form good hydrogen bonds with the maleic acid modified rosin resin, so that the adhesive strength of the coating adhesive is further improved.
Preferably, the ethylene embedding amount in the EVA emulsion is 20-25%.
By adopting the technical scheme, the property of the EVA emulsion can be changed by the embedding amount of the ethylene, and when the embedding amount of the ethylene is increased, the acetyl groups can be discontinuous, so that the mobility of the main chain of the polymer is increased, the fluidity is improved, and meanwhile, the cohesive strength is also reduced, so that the adhesive strength of the laminating adhesive is influenced. When the ethylene embedding amount is 20-25%, the adhesive liquid has good fluidity while ensuring enough cohesive strength.
Preferably, the EVA has a molecular weight of 4000-5000.
By adopting the technical scheme, better bonding capacity can be realized between the EVA and each component, and the adhesive solution has higher bonding strength on the premise of keeping good fluidity of the adhesive solution.
Preferably, the maleic acid modified rosin resin is maleic acid modified rosin pentaerythritol ester.
By adopting the technical scheme, the maleic acid modified rosin pentaerythritol ester has more hydroxyl groups with the same chemical environment, and can more effectively generate hydrogen bonds with the EVA emulsion, so that the adhesive strength of the adhesive solution is further improved.
Preferably, the raw materials also contain 7-10 parts by weight of diethyl phthalate.
By adopting the technical scheme, the diethyl phthalate can be used for adjusting the plasticity of the glue solution, the moving friction force of molecular chains is reduced, the flexibility and the fluidity of the polymer can be improved, the vacuum forming attaching effect is facilitated, and the cold resistance and the impact strength of the coagulated glue solution can be improved. And the diethyl phthalate can also improve the viscosity of the glue solution and further improve the adhesive strength of the glue solution.
Preferably, the raw material also contains 0.2 to 0.3 mass portion of sodium dodecyl benzene sulfonate.
By adopting the technical scheme, the sodium dodecyl benzene sulfonate has a surface activity effect, can adjust the particle size of the emulsion, and improves the dispersity of the emulsion in an aqueous solution, so that the emulsion is more uniformly contacted with an acting surface during adhesion, and the adhesive strength of the adhesive solution is further improved.
In a second aspect, the application provides a preparation process of a water-based PVC laminated adhesive for a paint-free door, which adopts the following technical scheme:
the process comprises the following steps:
s1: mixing hydroxyethyl cellulose with water according to the proportion of 1:5 and continuously stirring to obtain a hydroxyethyl cellulose colloid;
s2: mixing the rest water with the EVA emulsion, heating to 75-80 ℃, adding the aqueous polyurethane dispersion into the mixture, and stirring and mixing for 10-15min to obtain a first mixture;
s3: heating the first mixture to 110-115 ℃, adding the hydroxyethyl cellulose colloidal substance, fully mixing, and then adding diethyl phthalate and sodium dodecyl benzene sulfonate for mixing to obtain a second mixture;
s4: and respectively heating the second mixture and the maleic acid modified rosin resin to 170-175 ℃, uniformly mixing, adding the water-based aldehyde ketone resin into the mixture, stirring for 10-15min, and cooling to obtain the finished product of the laminating adhesive.
By adopting the technical scheme, in the mixing steps of S1 and S2, the hydroxyethyl cellulose and the water are mixed to form a colloid, and then the colloid is mixed with the EVA, so that the influence of the hydroxyethyl cellulose on the mixing uniformity of the aqueous polyurethane in the water absorption and expansion process can be prevented, the serious coating of colloidal particles formed by the hydroxyethyl cellulose on each component can be reduced, and the dispersibility of each component in the mixture can be improved. And different mixing temperatures are adopted in the mixing process of the components, so that the uniformity of the prepared glue solution can be improved, and the bonding strength of the prepared laminated glue is improved.
Preferably, in step S3, the hydroxyethyl cellulose gum is added in ten equal portions for 2-3 min.
By adopting the technical scheme, the hydroxyethyl cellulose colloid is added step by step, the dispersibility of the hydroxyethyl cellulose in the system is further improved, the serious coating effect of colloidal particles formed by the hydroxyethyl cellulose on each component is further reduced, and the bonding strength of the prepared coating adhesive is further improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the coating adhesive, water, EVA emulsion and aqueous polyurethane dispersion are used as base materials, and maleic acid modified rosin resin, aqueous aldehyde ketone resin and hydroxyethyl cellulose are added, so that the adhesive strength of the coating adhesive is improved.
2. The application provides the preferable ranges of the ethylene embedding amount and the molecular weight of the EVA emulsion, and the adhesive strength of the prepared laminating adhesive is further improved.
3. The raw materials of the emulsion also contain diethyl phthalate and sodium dodecyl benzene sulfonate, so that the plasticity and the dispersity of the emulsion are improved, and the adhesive strength of the laminated adhesive is further improved.
4. The application also provides a laminating adhesive process, and the prepared laminating adhesive has better uniformity and better bonding strength.
Detailed Description
Examples
Example 1: a water-based PVC laminated adhesive for a paint-free door,
the preparation method is characterized by comprising the following steps: 30kg of water, 90kg of EVA emulsion, 25kg of maleic acid modified rosin resin, 12kg of waterborne aldehyde ketone resin, 0.5kg of hydroxyethyl cellulose and 70kg of waterborne polyurethane dispersion. The EVA emulsion used has an ethylene insertion amount of 15% and a molecular weight of 3000; the maleic acid modified rosin resin is maleic acid modified rosin glyceride; the water-based aldehyde ketone resin is CT-50W resin; the hydroxyethyl cellulose is specifically Dow QP100 MH; the aqueous polyurethane dispersion specifically adopts PU-1601.
The preparation process comprises the following steps:
s1: mixing hydroxyethyl cellulose with water according to the proportion of 1:5 and continuously stirring to obtain a hydroxyethyl cellulose colloid;
s2: mixing the rest water with the EVA emulsion, heating to 75 ℃, adding the aqueous polyurethane dispersion into the mixture, and stirring and mixing for 10min to obtain a first mixture;
s3: heating the first mixture to 110 ℃, adding the hydroxyethyl cellulose colloid, and stirring to uniformly mix the hydroxyethyl cellulose colloid to obtain a second mixture;
s4: and respectively heating the second mixture and the maleic acid modified rosin resin to 170 ℃, uniformly mixing, adding the water-based aldehyde ketone resin into the mixture, stirring for 10min, and cooling to obtain the finished product of the laminating adhesive.
Example 2: a water-based PVC laminated adhesive for a paint-free door,
the difference from example 1 is that the amounts of the components are different, and the specific amounts are shown in table 1 below.
Example 3: a water-based PVC laminated adhesive for a paint-free door,
the difference from example 1 is that the EVA emulsion used has an ethylene insertion of 23%. The amounts of the remaining components are shown in Table 1 below.
Example 4: a water-based PVC laminated adhesive for a paint-free door,
the difference from example 1 is that the EVA emulsion used has a molecular weight of 4500. The amounts of the respective components of the zones are shown in table 1 below.
Example 5: a water-based PVC laminated adhesive for a paint-free door,
the difference from example 1 is that maleic acid modified rosin resin is specifically maleic acid modified rosin pentaerythritol ester, and the amounts of the components are shown in table 1 below.
Examples 6 to 7: a water-based PVC laminated adhesive for a paint-free door,
the difference from example 1 is that diethyl phthalate is contained in the raw material and the amounts of the components are shown in table 1 below.
Step S3 is: and heating the first mixture to 110 ℃, adding the hydroxyethyl cellulose colloid, fully mixing, and adding diethyl phthalate for mixing to obtain a second mixture.
Examples 8 to 9: a water-based PVC laminated adhesive for a paint-free door,
the difference from example 1 is that the raw material contains sodium dodecylbenzene sulfonate, and the amounts of the components are shown in table 1 below.
Step S3 is: and heating the first mixture to 110 ℃, adding the hydroxyethyl cellulose colloid, fully mixing, and then adding the sodium dodecyl benzene sulfonate for mixing to obtain a second mixture.
Example 10: a water-based PVC laminated adhesive for a paint-free door,
the difference from example 1 is that in step S3, the hydroxyethyl cellulose gum is added in ten equal portions at intervals of 2min, and stirred until well mixed after the addition is completed.
Table 1: examples 1-10 Components and amounts (kg)
Comparative example
Comparative example 1: an aqueous film-coated adhesive for furniture,
the preparation method is characterized by comprising the following steps: 15kg of deionized water, 40kg of triethyl citrate, 2kg of acrylate compounds, 10kg of functional auxiliary agents, 0.1kg of buffering agents, 2kg of emulsifying agents, 0.5kg of initiating agents, 0.1kg of oxidizing agents and 0.1kg of reducing agents.
The acrylic ester compound is a mixture of water-soluble amino resin and hydroxypropyl acrylate in the dosage ratio of 1: 1; the functional auxiliary agent is water-soluble acrylic resin; the emulsifier is polyvinyl butyral; the initiator is ammonium persulfate or potassium persulfate; the buffering agent is ammonium bicarbonate; the oxidant is tert-butyl hydroperoxide; the reducing agent is sodium formaldehyde sulfoxylate.
The preparation process comprises the following steps: deionized water, triethyl citrate, acrylate compounds, functional auxiliaries, a buffering agent, an emulsifying agent, an initiator, an oxidizing agent and a reducing agent are added into a stirrer and stirred at the temperature of 70 ℃ until the materials are uniformly mixed.
Comparative example 2: a water-based PVC laminated adhesive for a paint-free door,
the difference from example 1 is that the raw material does not contain maleic acid modified rosin glycerin ester, aqueous aldehyde ketone resin and hydroxyethyl cellulose. The amounts of the remaining components are shown in Table 2 below.
The preparation process comprises the following steps: and (3) mixing water and the EVA emulsion, heating to 75 ℃, adding the aqueous polyurethane dispersion into the mixture, and stirring and mixing for 10min to obtain the finished product of the laminating adhesive.
Comparative example 3: a water-based PVC laminated adhesive for a paint-free door,
the difference from example 1 is that the raw material does not contain maleic acid-modified rosin glycerin ester. The amounts of the remaining components are shown in Table 2 below.
Step S4 is: and heating the second mixture to 170 ℃, adding the water-based aldehyde ketone resin into the second mixture, stirring for 10min, and cooling to obtain the finished product of the laminating adhesive.
Comparative example 4: a water-based PVC laminated adhesive for a paint-free door,
the difference from example 1 is that the raw materials do not contain the aqueous aldehyde ketone resin. The amounts of the remaining components are shown in Table 2 below.
Step S4 is: and respectively heating the second mixture and the maleic acid modified rosin resin to 170 ℃, uniformly mixing the mixture, and cooling to obtain the finished product of the laminating adhesive.
Comparative example 5: a water-based PVC laminated adhesive for a paint-free door,
the difference from example 1 is that the starting material does not contain hydroxyethyl cellulose. The amounts of the remaining components are shown in Table 2 below.
The preparation process comprises the following steps:
s1: mixing water and EVA emulsion, heating to 75 ℃, adding the aqueous polyurethane dispersion into the mixture, and stirring and mixing for 10min to obtain a glue solution mixture;
s4: and (3) respectively heating the glue solution mixture and the maleic acid modified rosin resin to 170 ℃, uniformly mixing, adding the water-based aldehyde ketone resin into the mixture, stirring for 10min, and cooling to obtain the finished product of the laminating glue.
Table 2: COMPARATIVE EXAMPLES 2-5 Components and amounts (kg) thereof
Performance test since the main object of the present application is to improve the adhesive strength of a water-based type coating adhesive, a test is mainly performed around the adhesive strength.
The test principle is as follows: the PVC film is bonded on the wood board by using the water-based laminating adhesive, and then the bonding strength of the laminating adhesive to the PVC film and the wood board can be compared by detecting the 180-degree peel strength of the PVC film.
Test subjects: examples 1 to 10, comparative examples 1 to 5.
Sample preparation: the coated glue of each embodiment and each comparative example is uniformly coated on a solid wood composite board with the width of 25mm and the length of 250mm, the average thickness of the coated glue layer is 10 micrometers, the coating width is equal to the width of the solid wood composite board, and the coating length is 150 mm. The PVC film is adhered on the solid wood composite board by adopting a vacuum forming method, the thickness of the PVC film is 0.3mm, and the PVC film is trimmed after vacuum forming so as to have the same width with the solid wood composite board. And after the water-based laminated adhesive is naturally air-dried, the sample is manufactured. Five samples were prepared for each example and comparative example.
Test equipment: HZ-1005A microcomputer peeling tester.
The testing steps are as follows: according to the national standard GB/T2790-1995 of the people's republic of China, the average peeling force is measured by an HZ-1005A microcomputer peeling tester, and the chuck separation speed is 100 mm/min. Finally, the peel strength (kN/m) of the samples obtained in each of examples and comparative examples was calculated, and the average peel strength σ of each group of samples was calculated180°(kN/m), the result retains a decimal number, and the experimental results are shown in Table 3 below.
Table 3: average peel strength σ of samples prepared in examples 1 to 10 and comparative examples 1 to 5180°(kN/m)
Comparing the data of examples 1-2 with comparative example 1 in table 3, it can be seen that the peel strength of examples 1-2 is significantly greater than that of comparative example 1, thus demonstrating that the adhesive strength of the coated adhesive prepared in examples 1-2 is better than that of comparative example 1. This is because the maleic acid-modified rosin glycerin ester and the aqueous aldehyde ketone resin are added to the raw materials of examples 1 to 2, and these two components can generate hydrogen bonds having a large number and a large strength with water and EVA emulsion, respectively, and have a certain solubility per se and also improve the bonding strength between the components. On the other hand, the polyhydroxy structure of the maleic acid modified rosin glyceride and the water-based aldehyde ketone makes up the problem of organic matter dissolution in the water-based solvent, so that the content of effective bonding components in the system is increased while the fluidity of the system is maintained, and the overall bonding strength of the system is increased.
Comparing the data of examples 1-2 and comparative examples 2-4 in table 3, it can be seen that the peel strength of examples 1-2 is significantly greater than that of comparative examples 2-4, thus demonstrating that the adhesive strength of the coated adhesive prepared in examples 1-2 is better than that of comparative examples 2-4. In combination with the above analysis results, the maleic acid modified rosin glycerin ester and the water-based aldehyde ketone resin can further prove the function of improving the adhesive strength in the laminating adhesive.
Comparing the data of examples 1-2 and comparative example 5 in table 3, it can be seen that the peel strength of examples 1-2 is significantly greater than that of comparative example 5, thus demonstrating that the adhesive strength of the coated adhesive prepared in examples 1-2 is better than that of comparative example 5. This is because hydroxyethyl cellulose has good thickening and moisture-protecting effects and also maintains good fluidity of the system after addition of a large amount of organic components. And the cellulose can also form good hydrogen bonds with the maleic acid modified rosin resin, so that the adhesive strength of the coating adhesive is further improved.
Comparing the data of examples 1-2 and 3-4 in Table 3, it can be seen that the peel strength of examples 1-2 is lower than that of examples 3-4, indicating that the coated adhesive prepared in examples 3-4 has better adhesive strength than that of examples 1-2, and thus indicating that the EVA emulsion in examples 3-4 has better ethylene incorporation and molecular weight. This is because, when the ethylene insertion amount is increased, acetyl groups are discontinuous to increase the mobility of the main chain of the polymer and improve the fluidity, but the cohesive strength is also decreased to affect the adhesive strength of the coating adhesive. When the embedded amount of the ethylene is 20-25%, the adhesive liquid can have good fluidity while ensuring enough cohesive strength. Similarly, the EVA with too high molecular weight will affect the fluidity, and the EVA with too low molecular weight will affect the adhesive strength, so that the preferred molecular weight can improve the adhesive strength on the premise of ensuring the fluidity.
Comparing the data of examples 1-2 and 5 in Table 3, it can be seen that the peel strength of examples 1-2 is lower than that of example 5, indicating that the adhesive strength of the coated adhesive prepared in example 5 is better than that of examples 1-2. The reason is that the maleic acid modified rosin pentaerythritol ester has more hydroxyl groups with the same chemical environment, so that the hydrogen bond strength between the maleic acid modified rosin pentaerythritol ester, the EVA emulsion and water can be further improved, and the adhesive strength of the coating adhesive is improved.
Comparing the data of examples 1-2 and 6-7 in Table 3, it can be seen that the peel strength of example 1-2 is lower than that of examples 6-7, indicating that the adhesive strength of the coated adhesive prepared in examples 6-7 is better than that of examples 1-2. This is because diethyl phthalate was added in examples 6 to 7, and diethyl phthalate was used to adjust the plasticity of the glue solution, reduce the kinetic friction of the molecular chains, improve the flexibility and fluidity of the polymer, contribute to the vacuum forming effect, and improve the cold resistance and impact strength of the coagulated glue solution. And the diethyl phthalate can also improve the viscosity of the glue solution and further improve the adhesive strength of the glue solution.
Comparing the data of examples 1-2 and examples 8-9 in Table 3, it can be seen that the peel strength of example 1-2 is lower than that of examples 8-9, indicating that the adhesive strength of the coated adhesive prepared in examples 8-9 is better than that of examples 1-2. This is because the sodium dodecylbenzenesulfonate was added in examples 8 to 9. The sodium dodecyl benzene sulfonate has surface activity, can regulate the particle size of the emulsion and improve the dispersion degree of the emulsion in the aqueous solution, so that the emulsion is more uniformly contacted with an acting surface in adhesion, and the adhesive strength of the adhesive solution is further improved.
Comparing examples 1-2 and example 10 in Table 3, it can be seen that the peel strength of examples 1-2 is lower than that of example 10, indicating that the adhesive strength of the coated adhesive prepared in example 10 is better than that of examples 1-2. The reason is that the hydroxyethyl cellulose colloid is added step by step, so that the dispersibility of the hydroxyethyl cellulose in a system can be further improved, the serious coating effect of colloidal particles formed by the hydroxyethyl cellulose on each component can be further reduced, and the adhesive strength of the prepared coating adhesive can be further improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (4)
1. A water-based PVC laminated adhesive for a paint-free door is characterized by being prepared from the following raw materials in parts by mass:
30-35 parts of water;
95-100 parts of EVA emulsion;
25-30 parts of maleic acid modified rosin resin;
12-15 parts of water-based aldehyde ketone resin;
0.5-1 part of hydroxyethyl cellulose;
70-80 parts of an aqueous polyurethane dispersion;
the maleic acid modified rosin resin is maleic acid modified rosin pentaerythritol ester;
the raw material also contains 7-10 parts by weight of diethyl phthalate;
the raw materials also contain 0.2 to 0.3 mass portion of sodium dodecyl benzene sulfonate;
the preparation process of the water-based PVC laminated adhesive for the paint-free door is characterized by comprising the following steps of: the process comprises the following steps:
s1: mixing hydroxyethyl cellulose and water according to the proportion of 1:5 and continuously stirring to obtain a hydroxyethyl cellulose colloid;
s2: mixing the rest water with the EVA emulsion, heating to 75-80 ℃, adding the aqueous polyurethane dispersion into the mixture, and stirring and mixing for 10-15min to obtain a first mixture;
s3: heating the first mixture to 110-115 ℃, adding the hydroxyethyl cellulose colloidal substance, fully mixing, and then adding diethyl phthalate and sodium dodecyl benzene sulfonate for mixing to obtain a second mixture;
s4: and respectively heating the second mixture and the maleic acid modified rosin resin to 170-175 ℃, uniformly mixing, adding the water-based aldehyde ketone resin into the mixture, stirring for 10-15min, and cooling to obtain the finished product of the coating adhesive.
2. The water-based PVC laminated adhesive for the paint-free door according to claim 1, which is characterized in that: the ethylene embedding amount in the EVA emulsion is 20-25%.
3. The water-based PVC laminated adhesive for the paint-free door according to claim 1, which is characterized in that: the molecular weight of the EVA emulsion is 4000-5000.
4. The water-based PVC laminated adhesive for the paint-free door according to claim 1, which is characterized in that: in step S3, the hydroxyethyl cellulose gum is divided into ten equal portions and added for a plurality of times, and the time interval of each addition is 2-3 min.
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| CN107779140A (en) * | 2016-08-26 | 2018-03-09 | 江苏国胶化学科技有限公司 | A kind of aqueous laminating adhesive |
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Denomination of invention: A water-based PVC film adhesive for paint free doors and its preparation process Granted publication date: 20220715 Pledgee: Zhejiang Xiaoshan Rural Commercial Bank Co.,Ltd. Yinong Branch Pledgor: Hangzhou aonuowei decoration materials Co.,Ltd. Registration number: Y2024330001697 |