CN116239983A - Adhesive for impregnating adhesive film paper and preparation method thereof - Google Patents
Adhesive for impregnating adhesive film paper and preparation method thereof Download PDFInfo
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- CN116239983A CN116239983A CN202310009325.5A CN202310009325A CN116239983A CN 116239983 A CN116239983 A CN 116239983A CN 202310009325 A CN202310009325 A CN 202310009325A CN 116239983 A CN116239983 A CN 116239983A
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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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
- C08G18/42—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
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- 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
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- 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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- Health & Medical Sciences (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an adhesive for impregnating adhesive film paper and a preparation method thereof, wherein the adhesive comprises the following raw materials: the aqueous polyurethane dispersion comprises structural units derived from dihydric alcohol N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine. The adhesive has the characteristics of no formaldehyde, pollution resistance, easy permeation, high bonding strength, good flexibility and the like.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to an adhesive for impregnated bond paper and a preparation method thereof.
Background
Impregnated bond paper, also known as "melamine" paper, is a bond paper which is dried to a certain extent after impregnation of the printed decor paper with amino resin, has a certain resin content and volatile content, and can be glued to each other or to an artificial board substrate by hot pressing. With the rapid development and maturity of the decoration industry, the requirement of people on environmental protection is gradually increased, and people talk about 'aldehyde' color change. How to reduce free formaldehyde in the decorative board, and the preparation of high-performance impregnated bond paper becomes an industry hot spot.
Chinese patent publication No. 113584936A describes a UV coating for coating formaldehyde-free impregnated paper, which has good curing effect, and can be rapidly cured to form a net-shaped polymer surface layer under the irradiation of ultraviolet light when in use, but the UV coating is arranged on the amino resin surface layer, so that the application range of the impregnated paper can be widened, and the problem of formaldehyde release can not be fundamentally solved. CN 111411543A describes an adhesive for solvent-resistant adhesive film paper and a preparation method thereof, wherein the polyurethane emulsion has smaller particle size, smaller molecular weight and moderate viscosity, so that the impregnated adhesive can better penetrate into the paper, the problem of paper damage of paper impregnated by common resin adhesive is solved, and meanwhile, the adhesive coating amount of the impregnated adhesive film paper is improved. However, the solid content is low, the molecular weight is small, and the surface bonding strength is low. While CN114293402A provides formaldehyde-free hot-pressed impregnated decorative paper with no toxicity and smooth surface and a preparation method thereof. It has the problems of long dipping and curing time and low production efficiency.
At present, urea-formaldehyde glue or melamine-formaldehyde glue is widely used in the impregnating glue industry, related researchers are developing formaldehyde-free schemes, but the properties of permeability, bonding strength, pollution resistance and the like cannot be balanced, and the development of novel adhesives is urgent for industrial researchers.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an adhesive for impregnating adhesive film paper and a preparation method thereof, wherein the adhesive adopts a special aqueous polyurethane dispersion and has the characteristics of no formaldehyde, pollution resistance, easy permeation, high adhesive strength, good flexibility and the like.
In order to achieve the above object, the present invention has the following technical scheme:
the invention provides an adhesive for impregnating adhesive film paper, which comprises the following components in parts by weight:
the aqueous polyurethane dispersion contains structural units derived from dihydric alcohol N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine (CAS: 214362-07-9), and the structural units are shown in a formula 1:
the aqueous polyurethane dispersion according to the invention has a structural unit mass content of 0.5 to 5%, preferably 1 to 3.5%, derived from the diol N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine.
In the research process of the adhesive for impregnating adhesive film paper, the invention surprisingly finds that the polyol with methoxy silane in the side chain is introduced into the main chain by adding the dihydric alcohol N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxy-silicone propyl) ethylenediamine in the raw material during the preparation of the aqueous polyurethane dispersion, so that the crosslinking density can be improved, the pollution resistance and the wear resistance can be increased, and the adhesion to a base material can be increased by the hydroxy after methoxy hydrolysis in the structure, so that the adhesive strength is improved. In addition, the invention also discovers that polyether modified siloxane with a specific structure is selected as a penetrating agent to act synergistically, so that the surface tension of the adhesive can be reduced, the adhesive can easily penetrate into a substrate, defects are reduced, and the surface bonding strength is improved.
In the invention, the aqueous polyurethane dispersion is aqueous aliphatic polyurethane dispersion, the particle size is 50-150nm, and the solid content is 35-40%.
In the invention, the aqueous polyurethane dispersion is prepared by adding water for emulsification and removing solvent after the reaction of aliphatic diisocyanate, polyalcohol, optional chain extender, molecular weight control agent, hydrophilic monomer and the like, the preparation process of the aqueous polyurethane dispersion is a method disclosed in the prior art, the conditions of raw material types, raw material proportions, operation parameters and the like contained in the specific preparation process are not particularly limited, and the technical personnel can adopt any realizable method to prepare the aqueous polyurethane dispersion according to the needs based on the prior art; for example, can be prepared by referring to the methods disclosed in patent CN109337632A and the like;
in some specific examples, the aliphatic diisocyanate is selected from one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate trimer, preferably hexamethylene diisocyanate and/or dicyclohexylmethane diisocyanate.
In some specific examples, the polyol is a polyol (preferably glycol) composition comprising N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine, preferably a composition of N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine with one or more of polyethylene glycol-propylene glycol, polycaprolactone diol, polycarbonate diol, polypropylene glycol, polyethylene adipate diol, 1, 4-butanediol polyadipate diol, 1, 6-hexanediol adipate diol, neopentyl glycol polyadipate diol, more preferably a composition of N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine with 1, 4-butanediol polyadipate diol and/or 1, 6-hexanediol adipate diol;
wherein the average molecular weight of the poly (1, 4-butanediol adipate) glycol and the poly (1, 6-hexanediol adipate) glycol is 500-3000 g/mol, preferably 1000-2000g/mol;
preferably, the polyol composition has a polyol mass content of 2-15%, preferably 4-12% for N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine;
preferably, the molar ratio of aliphatic diisocyanate to polyol is 1:1-4, preferably 1:1.3-2.6;
in some specific examples, the chain extender is selected from the group consisting of active hydrogen-containing sulfonic acid type hydrophilic chain extenders, preferably one or more of sodium 1, 4-butanediol-2-sulfonate, sodium 2- (2-aminoethyl) aminopropanesulfonate, sodium 2- (2-aminoethyl) aminoethane sulfonate, and sodium 1, 2-dihydroxy-3-propane sulfonate, more preferably sodium 2- (2-aminoethyl) aminoethane sulfonate;
preferably, the molar ratio of chain extender to aliphatic diisocyanate is 1:20-40, preferably 1:27-38;
in some specific examples, the molecular weight control agent is selected from one or more of ethanolamine, diethanolamine, triethanolamine, preferably diethanolamine;
preferably, the molar ratio of the molecular weight control agent to aliphatic diisocyanate is 1:8-40, preferably 1:13-29;
in some specific examples, the hydrophilic monomer is a reactive, monofunctional, polyethoxy segment-containing component having a molecular weight of 500 to 3000g/mol; preferably a polyoxyalkylene ether comprising at least one hydroxyl group, and the polymeric units of the polyoxyalkylene ether are propylene oxide and/or ethylene oxide, more preferably ethylene oxide; preferably, the number of ethylene oxide units per molecule of the polyoxyalkylene ether is 4 to 200, more preferably 12 to 75;
preferably, the hydrophilic monomer is one or more of D-3403 of Tego Chemie company, ymerTM N120 of Perstop company, and MPEG1200 of Korean music company, more preferably MPEG1200 of Korean music company;
preferably, the molar ratio of hydrophilic monomer to aliphatic diisocyanate is 1:50-130, preferably 1:53-105;
in some specific examples, the reaction may be performed with or without a catalyst selected from organobismuth, organotin, etc., and a solvent selected from acetone, butanone, etc., which are all conventionally selected in the art, and the amount thereof is not particularly limited.
In the present invention, the penetrating agent is polyether modified siloxane, and the number of ethylene oxide units in each molecule is 2-20, more preferably one or more of silwet 618, RH-288 and Dow DC 193.
In the invention, the thickener is one or more selected from fumed silica, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, carbomer and lithium magnesium silicate, preferably lithium magnesium silicate.
In the invention, the wear-resistant agent is selected from one or more of silicon dioxide suspension, aluminum oxide suspension and organic silicon resin emulsion, preferably 45-55% organic silicon resin emulsion by mass fraction.
Another object of the present invention is to provide a method for preparing the adhesive for impregnating cellophane. The method comprises the following steps:
s1: preparing a pre-gel by dispersing a thickener and part of water;
s2: adding the aqueous polyurethane dispersion into a dispersing kettle, stirring (I), adding the penetrating agent, stirring (II), adding the wear-resisting agent, stirring (III), adding the pregel and the rest of water, stirring (IV), and regulating the viscosity to prepare the adhesive for impregnating the adhesive film paper.
In the invention, the dispersing condition of S1 is that the rotating speed is 2000-3000rpm, and the time is 15-25min.
In the invention, the content of the thickener in the pregel of S1 is 10-30wt%.
In the invention, the rotating speed of the stirring (I) in the step S2 is 300-500rpm; the stirring (II) is carried out at a rotating speed of 500-800rpm for 8-15min; the stirring (III) is carried out at a rotating speed of 300-500rpm for 8-15min; the stirring (IV) is carried out at a rotating speed of 500-800rpm for 10-25min.
In the present invention, the viscosity of S2 is adjusted to 30 to 500 mPas.
Compared with the prior art, the invention has the following positive effects:
1) Formaldehyde is not added, so that the release of formaldehyde to release polluted air is avoided, and the harm to human bodies is reduced;
2) The pollution resistance is good, and the crosslinking density is improved and the pollution resistance is improved by adding the polyol of methoxy silane;
3) The adhesive is easy to permeate, reduces the surface tension of the adhesive, enables the adhesive to permeate the substrate easily, reduces defects, improves surface bonding strength and improves production efficiency.
Detailed Description
Embodiments of the invention are further described below in connection with the examples, but the invention is not limited to the examples set forth and is intended to include any other well known modifications within the scope of the claimed invention.
In each example and comparative example of the present invention, the main raw materials were obtained by purchasing the following raw materials and reagents, if not specified, by the common commercial route:
PBA2000: polybutylene adipate, hydroxyl number 56mgKOH/g, number average molecular weight 2000, kagaku Kogyo Co., ltd.;
PHA2000: 1, 6-hexanediol adipate diol, hydroxyl number 56mgKOH/g, number average molecular weight 2000, kagaku chemical Co., ltd.;
n, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine: purity 95%, shanghai Dan Yang chemical Co., ltd;
HMDI: dicyclohexylmethane diisocyanate: the NCO content is more than or equal to 31.8 percent, and is a product of Wanhua chemical group Co., ltd;
HDI:1, 6-hexamethylene diisocyanate, NCO content about 50%, wanhua chemical group Co., ltd;
MPEG: polyethylene glycol monomethyl ether, hydroxyl value 46.75mgKOH/g, number average molecular weight 1200, functionality 1, korean music day;
diethanolamine: purity is more than or equal to 98 percent, and the Dow chemical;
wear-resistant aluminum oxide: super shares in ZC-L10;
wear-resistant silicone emulsion: h9608, hubei long-win the four seas;
thickener lithium magnesium silicate WS3: density 2300-2600kg/m 3 Germany Lei Fusi;
penetrant Silwet 618: the purity is more than or equal to 90 percent, and the new material is a new material for the maitui picture;
RH288: the purity is more than or equal to 90 percent, and the Zhejiang is wet;
penetrant DC 193: purity is more than or equal to 98 percent, and the Dow chemical;
thickener fumed silica: AEROSIL 200 with purity greater than or equal to 99% is a win in Germany.
Preparation example 1 (preparation of aqueous polyurethane dispersion i):
10g of dehydrated N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine, 200g of dehydrated polybutylene adipate PBA2000, 40g of dehydrated 1, 6-hexanediol adipate diol, 45g of hexamethylene diisocyanate, 15g of dicyclohexylmethane diisocyanate, 95g of acetone and 7.5g of MPEG are added into a 1L four-port round bottom flask equipped with a nitrogen inlet and outlet, the mixture is stirred at 85 ℃ for 3h until NCO% reaches 4.85%, 210g of acetone is added after cooling, 4.3. 4.3g A-95 (2- (2-aminoethyl) -2-aminoethanesulfonic acid, 4.2g of IPDA and 5.2g of 50% concentration diethanolamine aqueous solution are added under stirring for 10min, 615g of deionized water is added under rapid stirring for dispersion, and acetone is separated by distillation to obtain an aqueous polyurethane dispersion I with a particle size of 65nm and a solid content of 35.0wt%, wherein the content of units derived from the dihydric alcohol N, N '-bis (2-hydroxyethyl) -N, N' -trimethoxy ethylenediamine is 1% by mass.
Preparation example 2 (preparation of aqueous polyurethane dispersion ii):
30g of dehydrated N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine, 180g of dehydrated polybutylene adipate PBA2000, 40g of dehydrated 1, 6-hexanediol adipate diol, 28g of hexamethylene diisocyanate, 40g of dicyclohexylmethane diisocyanate, 95g of acetone and 12g of MPEG are added into a 1L four-necked round bottom flask with a nitrogen inlet and outlet, the mixture is stirred at 85 ℃ for 3h until NCO% reaches 3.58%, 220g of acetone is added after cooling, 3.3. 3.3g A-95 (2- (2-aminoethyl) -2-aminoethanesulfonic acid and 2.4g of 50% concentration diethanolamine aqueous solution are added under stirring for 10min, 566g of deionized water are added under stirring for dispersion, and then acetone is distilled off to obtain an aqueous polyurethane dispersion II with a particle diameter of 83nm and a solid content of 39.5wt%, wherein the structural unit derived from the dihydric alcohol N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine is 3.3%.
Preparation example 3 (preparation of aqueous polyurethane dispersion iii):
20g of dehydrated N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine, 150g of dehydrated polybutylene adipate PBA2000, 80g of dehydrated 1, 6-hexanediol adipate diol, 35g of hexamethylene diisocyanate, 12g of dicyclohexylmethane diisocyanate, 100g of acetone and 9.5g of MPEG are added into a 1L four-necked round bottom flask with a nitrogen inlet and outlet, the mixture is stirred at 80 ℃ for 3h until NCO% reaches 2.59%, 210g of acetone is added after cooling, 3.3g A-95 g of IPDA and 3.2g of 50% concentration diethanolamine aqueous solution are added under stirring for 10min, and 547g of deionized water is added under rapid stirring for dispersion. And then separating acetone by distillation to obtain the aqueous polyurethane dispersion III. The particle size was 105nm and the solid content was 37wt%, wherein the mass content of structural units derived from the diol N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine was 2.3%.
The main performance in the embodiment of the invention is tested by the following method: (see GB/T28995-2012, GB/T17657-2013, GB/T15102-2017)
1) Permeation time: immersing the base paper into the impregnating adhesive, and recording the time when the base paper is completely immersed;
2) Sizing amount: x= (m 2-m 1)/m 1X 100, wherein: x is the sizing amount, m1 is the mass of the base paper, and m2 is the weight of the impregnated bond paper after drying;
3) Table bonding strength: according to the method specified in GB/T17657-2013 at 4.16;
4) Crack resistance: according to the method specified in GB/T17657-2013 at 4.36;
5) Scratch resistance: according to the method specified in GB/T17657-2013, the load is 1.50N;
6) Abrasion resistance: according to the method specified in GB/T17657-2013 at 4.44;
7) Fracture angle resistance: bending the impregnated bond paper, and marking the maximum angle of the impregnated bond paper when the impregnated bond paper is not broken as a breakage-resistant crack angle;
8) Formaldehyde release amount: according to the method specified in GB/T17657-2013, 4.59;
9) Stain resistance: according to the method specified in GB/T17657-2013 at 4.41;
the main equipment information employed in the respective examples and comparative examples of the present invention is as follows:
1) Multifunctional dispersing machine: EDS1000, shanghai Pushen chemical machinery Co., ltd;
2) Universal testing machine: AI-7000M, high-speed rail detection;
3) Scratch tester: HY-IV, shanghai modern environmental engineering technologies Co., ltd;
4) Blowing dry box: GT-7024-EL, high-speed rail detection;
5) Constant temperature and humidity box: GPL-2, aispeck laboratory instruments (Guangdong) Inc.;
6) Tab er abrasion instrument: HY-768, taiwan Hengyu instruments Co., ltd.
Example 1
The adhesive is prepared from the following raw materials in parts by weight:
aqueous polyurethane dispersion I: 68.0g of the total weight of the powder,
Silwet 618：2.0g，
WS3：1.0g，
H9608：9g，
water: 20g.
Preparing an adhesive for impregnating the adhesive film paper:
s1: sequentially adding a thickener WS3 and deionized water into a high-speed dispersing machine, dispersing at 2500rpm for 20min, and preparing a pregelatinized gel with the concentration of 20wt% for later use;
s2: adding the aqueous polyurethane dispersion I into a dispersion kettle, wherein the rotation speed of a stirring shaft is 400rpm; adding a penetrating agent Silwet 618, and stirring for 15min, wherein the rotation speed of a stirring shaft is 600rpm; adding an antiwear agent H9608, and stirring for 12min, wherein the rotation speed of a stirring shaft is 500rpm; and finally adding the rest deionized water and the pregelatinized, stirring for 15min, adjusting the viscosity to 400 mPa.s at the rotation speed of a stirring shaft of 650rpm, and preparing the adhesive for impregnating the adhesive film paper.
Example 2
The adhesive is prepared from the following raw materials in parts by weight:
aqueous polyurethane dispersion II: 60g of the powder, which is prepared from the raw materials of the powder,
RH288：1g，
sodium carboxymethyl cellulose: 0.2g of the total weight of the powder,
H9608：15.0g，
water: 24.0g.
Preparing an adhesive for impregnating the adhesive film paper:
s1: sequentially adding thickener sodium carboxymethylcellulose and deionized water into a high-speed dispersing machine, dispersing at 3000rpm for 15min, and preparing a pregelatinized gel with a concentration of 15wt% for later use;
s2: adding the aqueous polyurethane dispersion II into a dispersion kettle, wherein the rotation speed of a stirring shaft is 300rpm; adding penetrating agent RH288, stirring for 10min, wherein the rotation speed of a stirring shaft is 400rpm; adding an antiwear agent H9608, and stirring for 15min, wherein the rotation speed of a stirring shaft is 500rpm; and finally adding the rest deionized water and pregelatinized, stirring for 10min, adjusting the rotation speed of a stirring shaft to 800rpm, and adjusting the viscosity to 53 mPa.s to prepare the adhesive for impregnating the adhesive film paper.
Example 3
The adhesive is prepared from the following raw materials in parts by weight:
aqueous polyurethane dispersion iii: 50.0g of the total weight of the powder,
DC 193：3.0g，
WS3：2g，
ZC-L10：5.0g，
water: 40.0g.
Preparing an adhesive for impregnating the adhesive film paper:
s1: sequentially adding a thickener WS3 and deionized water into a high-speed dispersing machine, dispersing at 3000rpm for 25min, and preparing a pre-gel with the concentration of 30wt% for later use;
s2: adding the aqueous polyurethane dispersion III into a dispersion kettle, wherein the rotation speed of a stirring shaft is 400rpm; adding penetrant DC 193, stirring for 8min, and setting the rotation speed of a stirring shaft to be 500rpm; adding an antiwear agent ZC-L10, and stirring for 8min, wherein the rotation speed of a stirring shaft is 800rpm; and finally adding the rest deionized water and the pregelatinized, stirring for 25min, adjusting the viscosity to 350 mPa.s with the rotation speed of a stirring shaft of 500rpm, and preparing the adhesive for impregnating the adhesive film paper.
Comparative example 1
Referring to example 3, the only difference is that: n, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine is not used in the preparation of the aqueous polyurethane dispersion III, and other parameters and operations are unchanged, so that the aqueous polyurethane dispersion III is prepared for the adhesive.
Comparative example 2
Referring to example 3, the only difference is that: when the aqueous polyurethane dispersion III is prepared, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine is replaced by double-end carbohydroxy-terminated silicone oil (SL 7520, chong Yao technology development Co., hangzhou), and other parameters and operations are unchanged, so that the adhesive is prepared.
Comparative example 3
Referring to example 3, the only difference is that: when the aqueous polyurethane dispersion III is prepared, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine is replaced by trimethoxy terminated polydimethylsiloxane (RH-FW 1K, ningbo Ruo He high new material technology Co., ltd.) and other parameters and operations are unchanged, so that the adhesive is prepared.
Comparative example 4
Referring to embodiment 1, the only difference is that: the penetrating agent is not used in the adhesive preparation process, and other parameters and operations are unchanged, so that the adhesive is prepared.
Comparative example 5
Referring to embodiment 1, the only difference is that: the adhesive is prepared without using an anti-wear agent in the preparation process of the adhesive, and other parameters and operations are unchanged.
Comparative example 6
Referring to embodiment 1, the only difference is that: the adhesive is prepared without using a thickening agent in the preparation process, and other parameters and operations are unchanged.
Comparative example 7
The comparative example is melamine impregnating adhesive
The melamine impregnating adhesive is prepared from the following raw materials in parts by weight:
aqueous melamine resin dispersion: 98g of the total weight of the powder,
germany Huoshi740: 0.5g of the total weight of the powder,
dioctyl sodium maleate sulfonate: 1.5g.
The aqueous melamine resin dispersion of this comparative example was prepared:
accurately weighing the components according to the proportion of the glue base material, adding water and formaldehyde solution into a reaction kettle, uniformly stirring, adding melamine powder, starting a stirrer to stir at the rotating speed of 1200 revolutions per minute, heating to 100 ℃, reacting the mixed solution for 100 minutes under stirring, adding caustic soda into the reaction kettle to adjust the pH value of the mixed solution to 9.0 when the water solubility multiple of the liquid is 1:3, cooling the glue base material mixed solution to 45 ℃, adding diethylene glycol, and uniformly stirring for later use;
the preparation method comprises the following raw materials in parts by weight:
55kg of water, 120kg of formaldehyde aqueous solution with the weight percentage concentration of 34%, 90kg of melamine powder and 18kg of diethylene glycol.
The adhesive prepared in the examples and the comparative examples is adopted to impregnate the base paper and dry the base paper at 130 ℃ to obtain impregnated bond paper; and hot-pressing the impregnated bond paper to the surface of the artificial board under the conditions of 8MPa,150 ℃ and 1min to obtain the artificial board with the decorative paper facing. The impregnating compound prepared in the above examples was tested according to national standards GB/T28995-2012, GB/T17657-2013 and GB/T15102-2017, and the test results are shown in Table 1.
Table 1 results of performance testing of various examples and comparative examples
Finally, it should be noted that the above embodiments are only described as preferred embodiments of the present invention, and not limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various modifications and improvements made to the technical solution of the present invention or equivalent substitutions should be made, all fall within the scope of the present invention as defined in the claims.
Claims (10)
1. An adhesive for impregnating adhesive film paper is characterized by comprising the following components in parts by weight:
the aqueous polyurethane dispersion contains structural units derived from the diol N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine.
2. The adhesive according to claim 1, characterized in that the aqueous polyurethane dispersion has a content of structural units derived from the diol N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine of 0.5 to 5%, preferably 1 to 3.5% by mass.
3. The adhesive according to claim 1 or 2, wherein the aqueous polyurethane dispersion is an aqueous aliphatic polyurethane dispersion having a particle size of 50-150nm and a solids content of 35-40%.
4. An adhesive according to any one of claims 1 to 3, wherein the aqueous polyurethane dispersion is prepared by reacting an aliphatic diisocyanate, a polyol, a chain extender, a molecular weight controlling agent, a hydrophilic monomer, emulsifying with water, and removing the solvent.
5. The adhesive according to any one of claims 1 to 4, wherein the aliphatic diisocyanate is selected from one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate trimer, preferably hexamethylene diisocyanate and/or dicyclohexylmethane diisocyanate;
the polyol is a polyol (preferably glycol) composition comprising N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine, preferably a composition of N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine and one or more of polyethylene glycol-propylene glycol, polycaprolactone glycol, polycarbonate glycol, polypropylene glycol, polyethylene glycol adipate glycol, 1, 4-butanediol polyadipate glycol, 1, 6-hexanediol adipate glycol, neopentyl glycol polyadipate glycol, more preferably a composition of N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine and 1, 4-butanediol polyadipate glycol and/or 1, 6-hexanediol polyadipate glycol; wherein the average molecular weight of the poly (1, 4-butanediol adipate) glycol and the poly (1, 6-hexanediol adipate) glycol is 500-3000 g/mol, preferably 1000-2000g/mol;
preferably, the polyol composition has a polyol mass content of 2-15%, preferably 4-12% for N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine;
the chain extender is selected from one or more of active hydrogen-containing sulfonic acid type hydrophilic chain extender, preferably 1, 4-butanediol-2-sodium sulfonate 2- (2-amino ethyl) sodium amino propane sulfonate, 2- (2-amino ethyl) sodium amino ethane sulfonate and 1, 2-dihydroxy-3-sodium propane sulfonate, more preferably 2- (2-amino ethyl) sodium amino ethane sulfonate;
the molecular weight control agent is selected from one or more of ethanolamine, diethanolamine and triethanolamine, preferably diethanolamine;
the hydrophilic monomer is a component which is reactive to isocyanate and has single functionality and contains a polyethoxy chain segment, and the molecular weight of the hydrophilic monomer is 500-3000 g/mol; preferably a polyoxyalkylene ether comprising at least one hydroxyl group, and the polymeric units of the polyoxyalkylene ether are propylene oxide and/or ethylene oxide, more preferably ethylene oxide; preferably, the number of ethylene oxide units per molecule of the polyoxyalkylene ether is 4 to 200, more preferably 12 to 75; preferably, the hydrophilic monomer is one or more of D-3403 of Tego Chemie company, ymerTM N120 of Perstop company, and MPEG1200 of Korean music company, more preferably MPEG1200 of Korean music company.
6. The adhesive of any one of claims 1-5, wherein the penetrating agent is a polyether modified siloxane having a number of ethylene oxide units per molecule of 2-20, more preferably one or more of silwet 618, RH-288, or dow DC 193.
7. The adhesive according to any one of claims 1 to 6, wherein the thickener is selected from one or more of fumed silica, sodium carboxymethylcellulose, hydroxypropyl methylcellulose, carbomers, lithium magnesium silicate, preferably lithium magnesium silicate.
8. The adhesive according to any one of claims 1 to 7, wherein the antiwear agent is selected from one or more of silica suspension, alumina suspension, silicone emulsion, preferably 45-55% silicone emulsion by mass.
9. A method for preparing an adhesive for impregnating a cellophane as claimed in any one of claims 1 to 8, comprising the steps of:
s1: preparing a pre-gel by dispersing a thickener and part of water;
s2: adding the aqueous polyurethane dispersion into a dispersing kettle, stirring (I), adding the penetrating agent, stirring (II), adding the wear-resisting agent, stirring (III), adding the pregel and the rest of water, stirring (IV), and regulating the viscosity to prepare the adhesive for impregnating the adhesive film paper.
10. The method according to claim 9, wherein the dispersing condition of S1 is a rotation speed of 2000-3000rpm for 15-25min;
s1, the content of the thickener in the pregel is 10-30wt%;
s2, the rotating speed of the stirring (I) is 300-500rpm; the stirring (II) is carried out at a rotating speed of 500-800rpm for 8-15min; the stirring (III) is carried out at a rotating speed of 300-500rpm for 8-15min; the stirring (IV) is carried out at a rotating speed of 500-800rpm for 10-25min;
s2, regulating the viscosity to 30-500 mPa.s.
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|---|---|---|---|---|
| US20190322793A1 (en) * | 2016-12-29 | 2019-10-24 | Wanhua Chemical Group Co., Ltd. | Polyurethane or polyurethane-urea aqueous dispersion, preparation method therefor, and use thereof |
| CN111117555A (en) * | 2019-12-30 | 2020-05-08 | 庄明磊 | Environment-friendly aqueous adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190322793A1 (en) * | 2016-12-29 | 2019-10-24 | Wanhua Chemical Group Co., Ltd. | Polyurethane or polyurethane-urea aqueous dispersion, preparation method therefor, and use thereof |
| CN111117555A (en) * | 2019-12-30 | 2020-05-08 | 庄明磊 | Environment-friendly aqueous adhesive and preparation method thereof |
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